WO2015187864A1

WO2015187864A1 - Thermal management of fluid storage and dispensing vessels

Info

Publication number: WO2015187864A1
Application number: PCT/US2015/034043
Authority: WO
Inventors: Glenn M. Tom; Mark Hendrickson
Original assignee: Entegris, Inc.
Priority date: 2014-06-03
Filing date: 2015-06-03
Publication date: 2015-12-10
Also published as: TW201603882A

Abstract

A fluid storage and dispensing apparatus is described, which provides a thermal input to a fluid storage medium during a latter stage of the fluid dispensing operation to effect enhanced removal of heels fluid from the storage medium, e.g., solid-phase physical adsorbent, ionic liquid, or other storage medium. A thermal management assembly is employed, which may utilize thermowell(s) in a fluid storage and dispensing vessel of the apparatus, with circulation of heat transfer fluid through the thermowell or with exothermic reaction of chemical heat generation source material in the thermowell. Alternatively, the thermal management assembly may comprise a vortex chiller arranged to heat the fluid storage medium to dispense heels fluid in a latter stage of the dispensing operation, with the vortex chiller optionally also being arranged to chill the adsorbent during charging and/or transport of the apparatus, to accommodate a high inventory of fluid in the fluid storage and dispensing vessel of the apparatus. Associated methodology is described, for increasing availability of dispensed fluid from a fluid storage and dispensing vessel holding adsorbent having fluid adsorbed thereon.

Description

THERMAL MANAGEMENT OF FLUID STORAGE AND DISPENSING

VESSELS

CROSS-REFERENCE TO RELATED APPLICATION

[0001] The benefit of priority under 35 USC 119 of U.S. Provisional Patent Application 62/007,384 filed June 3, 2014 in the names of Glenn M. Tom and Mark Hendrickson for "THERMAL MANAGEMENT OF FLUID STORAGE AND DISPENSING VESSELS" is hereby claimed. The disclosure of U.S. Provisional Patent Application 62/007,384 is hereby incorporated by reference, in its entirety, for all purposes.

FIELD

[0002] The present disclosure relates to thermal management of adsorbent-based fluid storage and dispensing apparatus, and more particularly to a fluid storage and dispensing apparatus comprising a thermal management assembly that is effective to significantly increase the amount of fluid that can be dispensed from a vessel containing an adsorbent medium on which the fluid is stored, and from which the fluid is desorbed under dispensing conditions. The disclosure also relates to an associated methodology for achieving reduced heels operation of an adsorbent-based fluid storage and dispensing apparatus.

BACKGROUND

[0003] Physical adsorbent-based gas storage and dispensing apparatus of the type 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. Such apparatus includes a vessel holding a physical adsorbent medium such as molecular sieve, activated carbon, or other adsorbent medium 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.

[0004] In such adsorbent-based gas storage and dispensing apparatus, 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 adsorbent medium and desorptively removed from such adsorbent 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 adsorbent medium itself (e.g., involving such parameters as adsorbent media size, shape, porosity, pore size distribution, and tortuosity of interior pore passages).

[0005] A specific problem encountered in the use of such adsorbent-based gas storage and dispensing apparatus is that it becomes disproportionately more difficult to desorb and dispense the fluid as the inventory of fluid in the vessel drops to residual levels. The pressure drop from the vessel to a downstream tool or flow circuitry may in fact become too low to support dispensing, with the result that a substantial amount of fluid remains as so-called "heels" on the adsorbent in the vessel when dispensing can no longer take place. This heels portion then is lost as "non-removable" fluid.

[0006] Thus, the fluid storage and dispensing vessel may be taken out of service with a significant quantity of fluid still in the vessel, e.g., 5-20% or more. This circumstance results in severely reduced gas utilization efficiency. A solution to such problem is needed.

SUMMARY

[0007] The present disclosure relates to thermal management of adsorbent-based fluid storage and dispensing apparatus, and associated methodology for achieving reduced heels operation of an adsorbent-based fluid storage and dispensing apparatus.

[0008] In one aspect, the disclosure relates to a fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel holding a storage medium for fluid, wherein the apparatus is adapted for dispensing fluid from the storage medium under dispensing conditions, and wherein the storage medium is responsive to heating to release stored fluid therefrom, the apparatus comprising a thermal management assembly that is constructed and arranged to input thermal energy to the storage medium after a period of dispensing so as to increase temperature of the storage medium above its temperature in prior dispensing, for enhanced release of fluid from the storage medium.

[0009] In another aspect, the disclosure relates to a fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel with an interior volume holding an adsorbent material having sorptive affinity for a fluid to be stored on and desorptively dispensed from such adsorbent material, and at least one thermowell arranged for thermal communication with the interior volume of the vessel, with said at least one thermowell being adapted for supply of a heat transfer fluid thereto for input of heat to the adsorbent material to effect desorption of adsorbed fluid therefrom.

[0010] In a further aspect, the disclosure relates to a fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel with an interior volume holding an adsorbent material having sorptive affinity for a fluid to be stored on and desorptively dispensed therefrom, and at least one thermowell arranged for thermal communication with the interior volume of the vessel, with such at least one thermowell being adapted for supply of chemically-generated heat to the adsorbent material to effect desorption of adsorbed fluid therefrom.

[0011] A further aspect of the disclosure relates to a fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel with an interior volume holding adsorbent having sorptive affinity for a fluid to be stored on and desorptively dispensed therefrom, and a vortex chiller that is arranged to be actuatable to provide heating of the adsorbent to enhance fluid desorption therefrom.

[0012] The disclosure relates in a further aspect to a fluid storage and dispensing apparatus comprising a fluid storage and dispensing vessel holding a storage medium for fluid on which fluid is stored and from which fluid is dispensed under dispensing conditions comprising thermal modulation of the storage medium, and a thermal management assembly arranged to thermally modulate the storage medium, wherein the thermal management assembly comprises at least one of a thermowell and a vortex chiller.

[0013] Yet another aspect of the disclosure relates to a method of increasing availability of dispensed fluid from a fluid storage and dispensing vessel holding adsorbent having fluid adsorbed thereon, comprising dispensing fluid from the vessel under dispensing conditions comprising desorption of fluid from the adsorbent, and providing a thermal input to the adsorbent to desorptively remove at least a portion of heels fluid from the adsorbent during a final portion of said dispensing. [0014] In another aspect, the disclosure relates to a method of reducing heels fluid in dispensing of fluid from adsorbent on which the fluid is adsorptively stored and from which the fluid is desorbed for dispensing, said method comprising use of a fluid storage and dispensing apparatus of the present disclosure.

[0015] Other aspects, features and embodiments of the disclosure will be more fully apparent from the ensuing description and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] FIG. 1 is a schematic depiction of an adsorbent-based fluid storage and dispensing apparatus, according to one embodiment of the present disclosure.

[0017] FIG. 2 is a schematic depiction of a fluid storage and dispensing apparatus including a thermal management assembly for chemically generating heat for enabling dispensing of heels fluid, according to one embodiment of the present disclosure.

[0018] FIG. 3 is a schematic depiction of a fluid storage and dispensing apparatus including a thermal management assembly for chemically generating heat for enabling dispensing of heels fluid, according to another embodiment of the present disclosure.

[0019] FIG. 4 is a schematic representation of a fluid storage and dispensing apparatus according to another embodiment of the disclosure, comprising a thermal management assembly including a vortex chiller.

DETAILED DESCRIPTION

[0020] The present disclosure relates to thermal management of adsorbent-based fluid storage and dispensing apparatus, to achieve low heels operation in dispensing of fluid. As a result of such thermal management, a larger portion of the volume of fluid that is originally charged to the fluid storage and dispensing vessel of such apparatus is able to be discharged from the vessel in dispensing operation, in relation to corresponding fluid storage and dispensing apparatus that do not employ such thermal management. This in turn enables the fluid storage and dispensing apparatus to remain in dispensing service for a longer period of time, reducing the number of change-outs of the fluid storage and dispensing apparatus to replace apparatus with exhausted fluid storage and dispensing vessels, reducing the inventory of fluid storage and dispensing apparatuses that are required to supply a given total quantity of fluid, reducing the number of deliveries of fluid storage and dispensing apparatus needed to supply a gas-utilization process facility, and decreasing the operating costs of such facility.

[0021] The disclosure of U.S. Patent No. 5,704,967 issued January 6, 1998 to Glenn M. Tom, et al. for "FLUID STORAGE AND DELIVERY SYSTEM COMPRISING HIGH WORK CAPACITY PHYSICAL SORBENT" is hereby incorporated herein by reference, in its entirety.

[0022] As used herein and in the appended claims, the singular forms "a", "and", and "the" include plural referents unless the context clearly dictates otherwise.

[0023] The thermal management approaches of the present disclosure address the problem of heels involving adsorption-based fluid storage and dispensing systems in which adsorbents are employed on which gas is held strongly enough so that it is difficult to desorptively remove fluid at high enough rate for useful delivery to associated fluid-utilizing processes when the amount of gas held on the adsorbent becomes small during the latter stages of the fluid dispensing operation.

[0024] Such heels problem is particularly acute in the use of adsorbent-based fluid supply apparatus in ion implantation applications, in which dopant gases are dispensed to an ion source chamber to form ionic species for the implantation. In these applications, dopant gas is stored on an adsorbent, e.g., carbon or molecular sieve adsorbent, contained in a gas cylinder vessel that is installed in a gas box of the ion implanter or alternatively arranged outside the ion implanter enclosure for remote delivery of dopant gas to the ionization chamber of the ion implanter. The thermal management system of the present disclosure addresses the heels problem in such ion implantation applications without change in the form factor of the gas supply apparatus, while accommodating the electrical character of the ion implantation installation in which the system operates at many KeV above ground.

[0025] The features, construction, operation, and characteristics of the fluid storage and dispensing apparatus of the present disclosure are described below with respect to illustrative embodiments.

[0026] In one aspect, the disclosure relates to a fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel holding a storage medium for fluid, wherein the apparatus is adapted for dispensing fluid from the storage medium under dispensing conditions, and wherein the storage medium is responsive to heating to release stored fluid therefrom, the apparatus comprising a thermal management assembly that is constructed and arranged to input thermal energy to the storage medium after a period of dispensing so as to increase temperature of the storage medium above its temperature in prior dispensing, for enhanced release of fluid from the storage medium. [0027] Such period of dispensing, prior to thermal input to increase temperature of the storage medium, may involve dispensing of 60% or more of the originally present fluid from the fluid storage and dispensing vessel, depending on the amount of "heels fluid" that would otherwise be unavailable in the absence of the thermal management assembly. Thus, the original inventory of fluid dispensed from the vessel before thermal input by the thermal management assembly to increase temperature of the storage medium above its prior operating temperature, may be 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or other amount of the original inventory of fluid. Alternatively stated, the thermal input may be commenced when the remaining portion of the original inventory of fluid in the vessel has been reduced to 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, or other remaining portion value, based on the amount of original inventory of fluid in the vessel prior to inception of dispensing operation. It will be recognized that the specific amount of heels fluid in the vessel will very among respective applications, depending on the identity and character of the thermally responsive storage medium, the fluid that is stored on such medium, and the efficiency of the prior dispensing operation in extracting fluid from the storage medium.

[0028] In one embodiment, the disclosure relates to a fluid storage and dispensing apparatus of the resin disclosure, wherein the thermal management assembly is constructed and arranged to input thermal energy to the storage medium after at least 60% of original fluid inventory in the fluid storage and dispensing vessel has been dispensed from the vessel.

[0029] All of the aforementioned percentages are percentages by volume, based on original fluid inventory volume.

[0030] Although the storage medium for containing fluid in the broad practice of the present disclosure is primarily described herein as comprising a solid-phase physical adsorbent, it will be appreciated that the scope of applicability of the present disclosure is not thus limited, but rather extends to and encompasses use of other storage media, such as ionic liquids, reversible chemical reaction media interactive with the fluid to be stored, and other media and materials having affinity and suitability as a storage medium for the fluid.

[0031] The storage medium when in the form of a solid-phase physical adsorbent may be of any suitable type, and may for example comprise silica, alumina, aluminosilicates, molecular sieves, carbon, macroreticulate polymers and copolymers, etc. In embodiments, the storage medium may comprise a nanoporous carbon adsorbent having porosity of suitable character for the storage of the fluid to be retained in and dispensed from the fluid storage and dispensing vessel containing such adsorbent. [0032] Such solid-phase physical adsorbent may be in any suitable form, including particulate or granular forms, or powder forms, or monolithic forms. As used herein, "monolithic" means that the solid-phase physical adsorbent 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.

[0033] In embodiments, the solid phase physical adsorbent may be in a monolithic form, comprising discs or pucks of adsorbent, e.g., a nanoporous carbon adsorbent.

[0034] 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.

[0035] The fluid in the fluid storage and dispensing vessel that is sorptively retained on the adsorbent, or otherwise stored on a storage medium, and desorbed under suitable desorbing conditions for dispensing of fluid, or otherwise released from the storage medium, 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.

[0036] In the fluid storage and dispensing apparatus of the present disclosure, the thermal management assembly may comprise a monitoring and control assembly that is arranged to monitor pressure of gas being discharged from the vessel and/or other variable(s) and/or condition(s) of or affecting said dispensing, and for responsively modulating the thermal energy input to maintain a predetermined level or character of the discharged gas pressure and/or other variable(s) and/or condition(s) of or affecting said dispensing.

[0037] In specific embodiments, the fluid storage and dispensing apparatus may utilize a storage medium comprising adsorbent, e.g., carbon adsorbent. The thermal management assembly may be constructed and arranged to input thermal energy to the storage medium after at least 60% of the original fluid inventory in the fluid storage and dispensing vessel has been dispensed from the vessel. As discussed hereinafter, the thermal management assembly may be or comprise a non- electrical assembly, e.g., of a pneumatic or other non-electrical character.

[0038] The fluid storage and dispensing apparatus in specific implementations may be coupled in fluid-supplying relationship to a fluid-utilization facility or tool, e.g., a semiconductor manufacturing facility or tool, such as an ion implantation tool.

[0039] The fluid storage and dispensing apparatus of the present disclosure may by way of example comprise a fluid storage and dispensing vessel holding a storage medium for fluid on which fluid is stored and from which fluid is dispensed under dispensing conditions comprising thermal modulation of the storage medium, and a thermal management assembly arranged to thermally modulate the storage medium, wherein the thermal management assembly comprises at least one of a thermowell and a vortex chiller.

[0040] As discussed hereinafter in greater detail, the thermal management assembly of the fluid storage and dispensing apparatus in specific embodiments may comprise a thermowell coupled with a source of heat transfer fluid for thermal modulation of the vessel and storage medium, e.g., adsorbent. In other embodiments, the thermal management assembly of the fluid storage and dispensing apparatus may comprise a thermowell containing a reactant, coupled with a source of co-reactant arranged so that the co-reactant is introduced to the thermowell to achieve exothermic reaction with the reactant therein, for supplying heat to the vessel and storage medium, e.g., adsorbent. In still other embodiments, the thermal management assembly of the fluid storage and dispensing apparatus may comprise a vortex chiller that is arranged to selectively provide heat or refrigeration input to the vessel and storage medium, e.g. adsorbent.

[0041] The fluid storage and dispensing apparatus of the disclosure may be constituted with the thermal management assembly comprising a monitoring and control assembly that is arranged to monitor pressure of gas being discharged from the vessel and/or other variable(s) and/or condition(s) of or affecting the dispensing, and for responsively modulating the thermal energy input to maintain a predetermined level or character of the discharged gas pressure and/or other variable(s) and/or condition(s) of or affecting the dispensing. [0042] The disclosure in one aspect relates to a fluid storage and dispensing apparatus including a fluid storage and dispensing vessel with an interior volume holding an adsorbent material having sorptive affinity for a fluid to be stored on and desorptively dispensed from such adsorbent material. The fluid storage and dispensing vessel includes at least one thermowell arranged for thermal communication with the interior volume of the vessel, with such at least one thermowell being adapted for supply of a heat transfer fluid thereto for input of heat to the adsorbent material to effect desorption of adsorbed fluid therefrom.

[0043] In such thermowell-equipped fluid storage and dispensing apparatus, the thermowell(s) may be located in corresponding port(s) in the fluid storage and dispensing vessel. The ports may for example be formed by drilling bore openings in the vessel and tapping the openings to provide threading therein that is matably engageable with complimentary threading on an outer thermowell surface. The thermowells then can be threadably engaged with the bore openings and coupled with a suitable source of heat transfer fluid. In such manner, a heat transfer fluid at elevated temperature can be circulated through the thermowells to transfer heat to the vessel and adsorbent contained therein, so that the adsorbent is heated to temperature effecting desorption of adsorbed fluid from the adsorbent so that it can be discharged from the vessel through a valve head assembly coupled to the vessel, or other discharge assembly or arrangement.

[0044] The thermowell-equipped fluid storage and dispensing apparatus may further comprise a monitoring and control assembly that is arranged to monitor pressure of fluid, e.g., gas, being discharged from the vessel, and/or other process variable(s)/condition(s) of the dispensing operation, and to responsively and controllably actuate a pump or other fluid driver to circulate hot heat transfer fluid through the thermowell(s) and heat the adsorbent for desorption of heels fluid therefrom.

[0045] Such monitoring and control assembly may for example be arranged so that when the output pressure reaches a lower control limit (the pressure declining with continued dispensing of fluid, as the heels portion is approached), the heating fluid is pumped through the thermowell(s) to raise the temperature of the adsorbent and release the heels fluid. The heating fluid may be controlled as to its specific temperature and/or flow rate, to provide a suitable heat transfer rate that is effective to achieve the desired heels fluid dispensing.

[0046] The locations of the thermowells in the fluid storage and dispensing vessel can be varied to provide an appropriate heat flux to the adsorbent in the vessel. For example, the thermowell(s) may be located so as to extend into the interior volume of the vessel at sidewall location(s) of the vessel, or at base or floor region(s) of the vessel, and/or at shoulder or neck region(s) of the vessel. [0047] The thermowells may be arranged so that a distal portion of the thermowell extends into the interior volume of the vessel, e.g., in contact with adsorbent material when the vessel is charged with same. The proximal portion of the thermowell may be positioned exteriorly of the vessel with coupling structure that accommodates engagement of the thermowell with flow circuitry for the heated fluid. The flow circuitry may for example include a coaxial conduit (tube- within-a-tube) including an inner flow passage for introduction of heated fluid to the thermowell, and an outer annular flow passage for withdrawal of fluid from the thermowell, so that the fluid is flowed through the thermowell at appropriate temperature and flow rate conditions to achieve the desired extent of desorption of adsorbed heels fluid from the adsorbent.

[0048] The disclosure in another aspect relates to a fluid storage and dispensing apparatus including a fluid storage and dispensing vessel with an interior volume holding an adsorbent material having sorptive affinity for a fluid to be stored on and desorptively dispensed from such adsorbent material. The fluid storage and dispensing vessel includes at least one thermowell arranged for thermal communication with the interior volume of the vessel, with such at least one thermowell being adapted for supply of chemically-generated heat to the adsorbent material to effect desorption of adsorbed fluid therefrom.

[0049] In this alternative arrangement, chemical heat generation source material is placed in the thermowell and actuated to chemically generate heat for transfer from the thermowell to the vessel and adsorbent contained therein to effect desorption of heels fluid from the adsorbent. Such chemical heat generation source material may be actuated to generate heat in any suitable manner. For example, the source material may be contacted with a co-reactant delivered to the thermowell at a controlled rate by a monitoring and control assembly that is arranged to introduce the co-reactant from a source of same in response to a monitored condition of the dispensing operation.

[0050] In one illustrative arrangement a source of co-reactant is provided, having a syringe pump coupled therewith. The syringe pump in turn is coupled to the thermowell by a co-reactant delivery line, with the syringe pump being modulated by the monitoring and control assembly in response to delivery pressure of the dispensed fluid from the fluid storage and dispensing apparatus.

[0051] In this manner, the diminution of dispensed fluid pressure during the latter portion of the dispensing operation is sensed by the monitoring and control assembly, e.g., by a pressure transducer disposed at the outlet port of the valve head assembly of the storage and dispensing apparatus. Such pressure sensing, if below a set point pressure value, causes the monitoring and control assembly to responsively and controllably regulate the syringe pump to introduce co- reactant to the thermowell. Exothermic reaction of the reactant in the thermowell and the added co-reactant then takes place.

[0052] In another arrangement, the co-reactant is a gas that is supplied in a pressurized container, coupled to a feed line having a flow control valve therein, with the monitoring and control assembly being arranged to translate a valve element in the flow control valve between fully open and fully closed positions in response to the sensing of dispensed fluid pressure, vapor pressure in the interior volume of the fluid supply and dispensing vessel, or other process condition(s) or variable(s) susceptible of monitoring to reflect the approach or occurrence of heels-limited capacity of fluid in the vessel.

[0053] The heat of exothermic reaction generated by contacting of the respective reactant in the thermowell and the co-reactant added to the reactant in the thermowell then is transmitted by the thermowell to the vessel and adsorbent therein, to heat the adsorbent and cause it to desorb heels fluid. The desorbed fluid is dispensed from the fluid storage and dispensing vessel, with the rate and extent of exothermic heating of the adsorbent being controlled so that the heels fluid is dispensed at a corresponding rate and pressure to maintain desired fluid dispensing conditions.

[0054] In one specific embodiment, the chemical heat generation source material placed in the thermowell is sodium metal and the co-reactant is oxygen gas. These two reactants may be separated from one another in any suitable manner to prevent premature reaction thereof. Separation elements for such purpose may include valves, resealable septums, or any other suitable separation devices or subassemblies.

[0055] In the aforementioned example, wherein sodium metal is the reactant disposed in the thermowell, and oxygen is the co-reactant introduced to the thermowell to initiate an exothermic reaction, the monitoring and control assembly may include a vapor pressure monitor adapted to measure vapor pressure in the fluid supply vessel. When vapor pressure as measured by the pressure monitor, e.g., a pressure transducer, drops below a predetermined setpoint pressure level, the oxygen co-reactant is pulsed into the thermowell, to initiate the exothermic reaction

4Na + 0₂→ 2Na₂0 + heat.

The heat produced by this reaction then is transmitted from the thermowell to the vessel and adsorbent therein so that the heated adsorbent releases the heels fluid as desorbate.

[0056] By controlling the rate of addition of co-reactant gas, the rate of heat introduced into the adsorbent vessel can be modulated. Sodium is advantageous as a chemical heat generation source material because of its large heat of reaction with oxygen. This reaction is not very fast, and can be increased is necessary or desirable in specific applications, by using Na/K eutectics as the source material. In embodiments, the Na or Na/K chemical heat generation source material can be placed in a permeable sleeve in the thermowell to enable ready changeout of such reactant.

[0057] The present disclosure further contemplates a method of increasing availability of dispensed fluid from a fluid storage and dispensing vessel holding adsorbent having fluid adsorbed thereon, comprising dispensing fluid from the vessel under dispensing conditions comprising desorption of fluid from the adsorbent, and providing a thermal input to the adsorbent to desorptively remove at least a portion of heels fluid from the adsorbent during a final portion of said dispensing. In such method, the final portion of the dispensing may comprise dispensing when less than 40% by volume of fluid initially present in the vessel remains, e.g., when less than 30%, 20%, 10%, 5%, or other amount of fluid initially present in the vessel remains.

[0058] The thermal input in such method may be provided from a thermowell disposed in an interior volume of the fluid storage and dispensing vessel. The thermowell may be in contact with at least a portion of the adsorbent. Alternatively, the thermal input may be provided by an exothermic chemical reaction, or by a vortex chiller.

[0059] The present disclosure also contemplates a method of reducing heels fluid in dispensing of fluid from adsorbent on which the fluid is adsorptively stored and from which the fluid is desorbed for dispensing, in which the method comprises use of a fluid storage and dispensing apparatus of the present disclosure, as variously described herein, in any of the various embodiments thereof.

[0060] Referring to FIG. 1 , there is shown a schematic depiction of an adsorbent-based fluid storage and dispensing apparatus according to one embodiment of the present disclosure. The fluid storage and dispensing apparatus comprises a fluid storage and dispensing vessel 10 defining an interior volume therewithin for holding adsorbent (not shown for ease of description) on which fluid is to be stored and from which fluid is desorbed under dispensing conditions. The vessel 10 at its upper end portion is joined to a valve head assembly 12 containing one or more valve element(s) for controlling discharge of fluid from the vessel. A thermowell 14 of elongate character is disposed in the interior volume of the vessel 10 as shown, extending centrally upwardly in the interior volume from the lower end portion of the interior volume to an upper end portion thereof. Fluid flow circuitry is coupled with the thermowell, coupled to a suitable source of heating fluid (not shown) for introducing heated fluid to the thermowell from a heated fluid inlet 16 of the flow circuitry. The introduced heated fluid flows through the thermowell and passes to the heated fluid outlet 18 of the fluid flow circuitry. In this manner, the heated fluid effects heat transfer to the adsorbent in the interior volume of the vessel 10, with temperature of the heated fluid and/or flow rate of the heated fluid being controlled to regulate the outlet pressure and achieve enhanced dispensing of heels fluid.

[0061] The thermowell 14 thus can be provided in the vessel with coupling or engagement structure that at the point of use can be interconnected with heated fluid flow circuitry, e.g., by threaded mating structure, connection members, or other coupling elements or arrangements. The use of a heating fluid in this manner obviates electrical isolation issues associated with deployment of the fluid storage and dispensing apparatus in ion implantation installations involving high voltage ionization components.

[0062] FIG. 2 and FIG. 3 are schematic depictions of a fluid storage and dispensing apparatus including a thermal management assembly for chemically generating heat for enabling dispensing of heels fluid. The apparatus comprises a fluid storage and dispensing vessel 20 defining an interior volume in which an adsorbent, e.g., a solid phase physical adsorbent such as carbon, molecular sieve, silica, or other adsorbent, is held. Corresponding structures and features in FIGS. 2 and 3 are correspondingly numbered.

[0063] The fluid storage and dispensing vessel 20 in FIGS. 2 and 3 is connected at its upper neck portion to a valve head assembly 22 arranged for selectively dispensing fluid from the vessel. The vessel is constructed with a central, axially extending thermowell 24, wherein the thermowell holds a chemical reaction heat source reagent, e.g., a reductant such as sodium metal, that is reactive with a co-reactant, e.g., an oxidant such as oxygen.

[0064] In FIG. 2, the thermowell at its lower end is coupled with an oxidant inlet valve 26, which in turn is joined to a supply of oxidant (not shown), such as a pressurized supply container of oxygen gas and associated flow circuitry (also not shown) interconnecting the oxidant inlet valve 26 and the oxygen gas supply container.

[0065] In FIG. 3, the thermowell at its lower end is coupled with a septum isolation device 28 that is joined to a supply of oxidant that is arranged in feed relationship to the septum isolation device, so that oxidant may be selectively flowed into the thermowell from the oxidant supply, via the septum isolation device, as actuated to establish flow communication between the oxidant supply and the thermowell.

[0066] When the oxidant is introduced and contacted with the reductant in the thermowell, the resulting exothermic reaction generates heat that is transferred from the thermowell to the adsorbent and the vessel 20. In consequence, the heels fluid held on the adsorbent will be desorbed by the transferred heat, so that the heels fluid can be dispensed from the vessel of the fluid storage and dispensing apparatus, to achieve extended operation at appropriate pressure dispensing conditions, in relation to a corresponding fluid storage and dispensing apparatus lacking the thermal management assembly of the present disclosure.

[0067] The disclosure in another aspect relates to a fluid storage and dispensing apparatus comprising a thermal management assembly comprising a vortex chiller that is actuatable to provide heating of adsorbent to enhance heels fluid desorption therefrom, and dispensing of such heels fluid. More generally, the vortex chiller is actuatable to provide heating or cooling of the adsorbent, as desired for dispensing (involving heating to desorb heels fluid) or for initial charging and/or subsequent storage of fluid on the adsorbent (involving cooling to enhance sorptive capacity for the fluid).

[0068] The vortex chiller of the present disclosure, also referred to as a vortex tube or as a Ranque-Hilsch vortex tube, mechanically separates compressed gas into hot and cold streams, and utilizes no moving parts. The hot stream can be at temperature of up to 200°C or higher, and the cold stream can be at temperature as low as -50°C or lower. In the operation of a vortex chiller, pressurized gas injected tangentially into a swirl chamber is rotationally accelerated and passes down the tube to an end having a conical nozzle that enables only the outer portion of the spinning stream to be discharged as a hot stream, and the inner portion is counter-axially directed to an opposite end of the tube to a conically divergent outlet cold stream.

[0069] The compressed gas fed to the swirl chamber of the vortex tube may be air or other working fluid, at pressure that may for example be on the order of 5-8 bar and the compressed gas may be accelerated by the swirl chamber so that it achieves a rotational speed of up to 10⁶ revolutions per minute or even higher.

[0070] In thermal management application in the adsorbent-based fluid storage and dispensing apparatus, the vortex chiller may be arranged so as to input heat or alternatively to input cooling to the adsorbent. The vortex chiller may be integrated with the fluid storage and dispensing apparatus, in any suitable manner. In embodiments, the adsorbent in the fluid storage and dispensing vessel may be arranged in contact with a sleeve or an internal chamber, e.g., a thermowell, or other chamber in the interior volume of the vessel, or a chamber or sleeve provided exteriorly of the vessel with the vessel disposed therein, or other arrangement in which the adsorbent is in heat transfer relationship to the working fluid being thermally managed by the vortex chiller. The thermowell, sleeve, or other chamber may be supplied by the vortex chiller with chilled heat transfer fluid during initial charging and subsequent storage of fluid on the adsorbent, so that a high capacity of adsorbed fluid can be stored on the adsorbent. At the point of use of the adsorbed fluid, the fluid is desorbed from the adsorbent by cessation of the chilling action, and with the vortex chiller then being used in a heating modality to provide heated heat transfer fluid at elevated temperature to the thermowell, sleeve, or other chamber, for heating of the adsorbent during the dispensing operation, so that heels fluid is efficiently dispensed from the fluid storage and dispensing vessel during the latter stages of the dispensing operation.

[0071] In one embodiment, a sleeve is utilized on the fluid storage and dispensing vessel, which receives fluid that is chilled or heated by a vortex chiller, depending on whether the vessel is being charged or maintained in a storage mode, or whether the vessel is being utilized to supply fluid in an active dispensing operation.

[0072] It will be recognized that the fluid storage and dispensing apparatus comprising a vortex chiller may be arranged in a wide variety of specific arrangements, to achieve enhanced adsorbent performance, and to substantially increase the working capacity of the adsorbent (i.e., the volume of the sorbate fluid adsorbent that is able to be adsorbed on, and subsequently dispensed from, the adsorbent, per unit weight or volume of the adsorbent).

[0073] FIG. 4 is a schematic representation of a fluid storage and dispensing apparatus according to another embodiment of the disclosure, comprising a thermal management assembly including a vortex chiller.

[0074] As illustrated in FIG. 4, the fluid storage and dispensing apparatus includes a fluid storage and dispensing vessel 30 coupled at its upper end to a fluid dispensing valve 34, which may be part of a valve head assembly for the vessel. The fluid dispensing valve 34 is in turn coupled to a fluid discharge line 36 for dispensing fluid to a downstream fluid-utilizing process system (not shown in FIG. 4), such as an ion implantation apparatus.

[0075] The fluid storage and dispensing vessel 30 is disposed in a sleeve or thermal cowling 32 forming a reservoir for flow of heat transfer fluid over the exterior wall of the vessel. A thermal management assembly 44 of the fluid storage and dispensing apparatus includes a vortex chiller 48 in a heat transfer fluid flow circuit comprising a hot fluid line 52 and a cold fluid line 50 joined to respective ends of the vortex chiller as shown. The vortex chiller is arranged in this embodiment to receive compressed air. The vortex chiller may be arranged to provide heated air to the hot fluid line at temperature that may for example be on the order of 130°C and chilled air to the cold fluid line at temperature that may be on the order of -47°C. A diverter valve 46 is provided to selectively allow flow of either hot air from the hot fluid line, or chilled air from the cold fluid line to the thermal fluid management feed line 54 for flow to the thermal cowling 32, depending on the selected setting of the diverter valve for heating or cooling of the vessel 30.

[0076] The fluid discharge line 36 in the FIG. 4 embodiment is provided with a monitoring and control assembly including a pressure transducer 38 that is arranged to monitor the pressure of the dispensed fluid in fluid discharge line 36. The pressure transducer is arranged to provide a monitoring signal that is transmitted in signal transmission line 40 to the pressure controller 42. The pressure controller 42 is arranged to control the compressed air supply to the vortex chiller 48 as well as the diverter valve 46.

[0077] In such manner, the fluid storage and dispensing vessel is heated or cooled as necessary. For example, cooling may be employed to maintain temperature of the adsorbent in vessel 30 at a low temperature to maximally load the adsorbent with fluid for subsequent use, during charging of the vessel with fluid in the first instance. Heating of the vessel with the heated from hot fluid line 50 during the latter stages of dispensing operation in order to dispense heels fluid from the adsorbent may be utilized, with the pressure transducer sensing a diminution of pressure in the fluid discharge line 36 as the heels portion of the adsorbed fluid becomes an increasingly large portion of the fluid inventory in the vessel.

[0078] This reduction of pressure as sensed by the pressure transducer will cause a corresponding sensing signal to be transmitted in signal transmission line 40 to the pressure controller, which responsively will cause compressed air to the flowed to the vortex chiller to generate heated fluid. The heated air flows in the hot fluid line 50 to the diverter valve, which is opened by the pressure controller to allow flow of the heated air to pass into the thermal fluid management feed line 54 for flow to the thermal cowling 32. The heated air in the thermal cowling heats the vessel 30 and the vessel conductively heats the adsorbent in the vessel so that heels fluid in the vessel remaining on the adsorbent is desorbed and dispensed from the vessel. Such dispensed fluid flows through the fluid dispensing valve 34 to the fluid discharge line 36 at sufficient rate to raise the pressure in the fluid discharge line to a desired set point level.

[0079] In an illustrative embodiment, the fluid storage and dispensing apparatus shown in FIG. 4 is installed and coupled to a downstream fluid-utilizing facility, e.g., by coupling to fluid dispensing line 36 or other arrangement for dispensed fluid delivery. The pressure transducer 38 reads the line pressure during the dispensing operation, with fluid dispensing valve 34 in an open position and fluid being desorbed from the adsorbent in the fluid storage and dispensing vessel 30, e.g., by pressure differential with the fluid dispensing line 36 being at lower pressure than pressure of the internal volume in the vessel. If the pressure in the fluid dispensing line 36 rises above a predetermined set point pressure level, compressed air is fed to the vortex chiller 48, by corresponding operation of the pressure controller 42 receiving the pressure sensing signal from pressure transducer 38 in signal transmission line 40. Concurrently, the diverter valve 46 is controlled to feed cold air, e.g., at temperature of 46°C, through the thermal cowling 32 to lower the temperature of the vessel 30 and adsorbent contained therein, and therefore the pressure will be adjusted to the set point pressure level. [0080] At the end stage of the fluid dispensing process, compressed air will be fed to the vortex chiller and the diverter valve 46 will be adjusted to flow heated air around the vessel 30 to increase the fluid delivery pressure, to maintain the set point pressure level in fluid dispensing line 36.

[0081] In this manner, the thermal management system enables higher levels of stored fluid to be dispensed from the adsorbent in the vessel than is possible in the absence of such thermal management system.

[0082] The pressure controller in the thermal monitoring and control assembly may be of a pneumatic character, involving no electrical power supplies or components, so as to accommodate applications such as ion implantation in which electrical devices present difficulties in respect of voltage differentials and isolation requirements. The pressure controller may thus comprise fluidic control components and subassemblies that are operatively arranged to maintain a set point pressure of the fluid dispensed from the fluid storage and dispensing vessel, with the pressure controller configured to actuate the vortex chiller to provide the thermal conditions that provide enhanced dispensing of heels fluid that would otherwise be unavailable for use.

[0083] In applications in which such electrical componentry is usefully employed, the pressure controller may be of an electrical, or other, character, controlling the vortex chiller to achieve the improved utilization of heels fluid. For such purpose, the controller may comprise microprocessors, programmable logic controllers, special purpose programmably arranged computers, or any other controller devices or assemblies that provide the required thermal management in the fluid storage and dispensing apparatus.

[0084] Although illustratively shown as utilizing pressure control of dispensed fluid in the specific embodiment of FIG. 4, it will be appreciated that other operating variables or parameters may be employed in the control scheme in a given application, such as flow rate, adsorbent temperature, pressure in the interior volume of the fluid storage and dispensing vessel, etc.

[0085] In addition, it will be recognized that in specific embodiments in which the fluid is desorbed by passage of a carrier gas through the interior volume of the fluid storage and dispensing vessel for contacting the adsorbent therein with the carrier gas, to effect desorption via concentration gradient, the carrier gas can be heated by the vortex chiller prior to passage through the vessel interior volume. In this manner, the carrier gas may be heated to appropriate temperature to release the adsorbed heels fluid to enhance dispensing thereof from the vessel.

[0086] If the carrier gas heated in such manner produces a gas mixture of desorbed adsorbate gas and carrier gas that is at temperature above the use temperature desired for the dispensed gas mixture, the gas mixture can then be passed in heat exchange relationship with chilled carrier gas produced by the vortex chiller to achieve the desired temperature for end use utilization, so that both hot and cold streams of gas produced by the vortex chiller operation are employed. The carrier gas in such instance may be of any suitable composition appropriate to the end use of the gas mixture. For example, the carrier gas may comprise a noble or other inert gas, such as nitrogen, helium, argon, krypton, etc., that is non-adsorbed, or a gas that is displacingly adsorbed by the specific adsorbent employed (i.e., being preferentially adsorbed by the adsorbent so as to displace the adsorbate fluid stored on the adsorbent).

[0087] It will be recognized that the thermal management assembly in the fluid storage and dispensing apparatus of the present disclosure may be configured and operated in a variety of suitable arrangements, and that the desired thermal management for enhanced extraction of heels fluid from the adsorbent may be effected with ancillary features and components, in relation to the generalized approaches herein described. For example, when a thermowell or other thermal management chamber is provided in an interior volume of a fluid storage and dispensing vessel, such interior member may be provided with secondary heat transfer capability, e.g., fins or other secondary heat exchange surface, to enhance the effectiveness and efficiency of the thermal management assembly.

[0088] The thermal management assembly of the present disclosure enables a high level of flexibility in storage and transport of the fluid storage and dispensing apparatus. For applications such as ion implantation, the dopant gas supplied from the adsorbent-containing fluid storage and dispensing vessel is desirably at subatmospheric pressure. The thermal management assembly of the present disclosure can be utilized for such applications, with the fluid storage and dispensing vessel being charged with dopant fluid at super-atmospheric pressure. The adsorbent-based fluid storage and dispensing apparatus then could be stored and transported with the fluid in the vessel at subatmospheric pressure, with the thermal management assembly being actuated at the point of use to chill the vessel and contained adsorbent, so that fluid can be dispensed from the chilled vessel and adsorbent at subatmospheric pressure.

[0089] As another variation of use of the thermal management assembly of the present disclosure, the thermal management assembly could be actuated at the fill station where the vessel is initially charged with fluid, to chill the vessel and adsorbent, to increase the adsorbent loading relative to charging at ambient or other higher temperature. Thereafter, the vessel in the fluid storage and dispensing apparatus could be maintained at cold temperature by the thermal management assembly, e.g., during storage and transport, or the vessel as originally charged in a chilled condition, could be packed in an insulated or super-insulated transport container, optionally with supplemental refrigerant capability, such as dry ice, liquefied nitrogen as a cold source, or mechanical refrigeration, or supplemental adsorption refrigeration assembly. In this manner, the vessel and adsorbent can be maintained at the chilled temperature until fluid dispensing is desired, and optionally thereafter during the dispensing operation.

[0090] Thus, the fluid storage and dispensing apparatus of the present disclosure, utilizing a thermal management assembly, can be flexibly tailored to specific application requirements, with pressure of dispensed fluid being modulated in a variety of alternative and/or additive approaches.

[0091] While the disclosure has been set forth herein in reference to specific aspects, features and illustrative embodiments, it will be appreciated that the utility of the disclosure is not thus limited, but rather extends to and encompasses numerous other variations, modifications and alternative embodiments, as will suggest themselves to those of ordinary skill in the field of the present disclosure, based on the description herein. Correspondingly, the disclosure as hereinafter claimed is intended to be broadly construed and interpreted, as including all such variations, modifications and alternative embodiments, within its spirit and scope.

Claims

THE CLAIMS What is claimed is:

1. A fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel holding a storage medium for fluid, wherein the apparatus is adapted for dispensing fluid from the storage medium under dispensing conditions, and wherein the storage medium is responsive to heating to release stored fluid therefrom, the apparatus comprising a thermal management assembly that is constructed and arranged to input thermal energy to the storage medium after a period of dispensing so as to increase temperature of the storage medium above its temperature in prior dispensing, for enhanced release of fluid from the storage medium.

2. The fluid storage and dispensing apparatus of claim 1, wherein the storage medium comprises adsorbent.

3. The fluid storage and dispensing apparatus of claim 2, wherein the adsorbent comprises a carbon adsorbent.

4. The fluid storage and dispensing apparatus of claim 1, wherein the thermal management assembly is constructed and arranged to input thermal energy to the storage medium after at least 60% of original fluid inventory in the fluid storage and dispensing vessel has been dispensed from the vessel.

5. The fluid storage and dispensing apparatus of claim 1, wherein the thermal management assembly is a non-electrical assembly.

6. The fluid storage and dispensing apparatus of claim 1, wherein the thermal management assembly is a pneumatic operation assembly.

7. The fluid storage and dispensing apparatus of claim 1, as coupled in fluid-supplying relationship to a fluid-utilization facility or tool.

8. The fluid storage and dispensing apparatus of claim 7, wherein the fluid-utilization facility comprises a semiconductor manufacturing facility or tool.

9. The fluid storage and dispensing apparatus of claim 8, wherein the semiconductor manufacturing facility or tool comprises an ion implantation tool.

10. The fluid storage and dispensing apparatus of claim 1, wherein the thermal management assembly comprises a thermowell coupled with a source of heat transfer fluid for thermal modulation of the vessel and storage medium.

1 1. The fluid storage and dispensing apparatus of claim 1 , wherein the thermal management assembly comprises a thermowell containing a reactant, coupled with a source of co-reactant arranged so that the co-reactant is introduced to the thermowell to achieve exothermic reaction with the reactant therein, for supplying heat to the vessel and storage medium.

12. The fluid storage and dispensing apparatus of claim 1, wherein the thermal management assembly comprises a vortex chiller that is arranged to selectively provide heat or refrigeration input to the vessel and storage medium.

13. The fluid storage and dispensing apparatus of claim 1, wherein the thermal management assembly comprises a monitoring and control assembly that is arranged to monitor pressure of gas being discharged from the vessel and/or other variable(s) and/or condition(s) of or affecting said dispensing, and for responsively modulating the thermal energy input to maintain a predetermined level or character of the discharged gas pressure and/or other variable(s) and/or condition(s) of or affecting said dispensing.

14. A fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel with an interior volume holding an adsorbent material having sorptive affinity for a fluid to be stored on and desorptively dispensed from such adsorbent material, and at least one thermowell arranged for thermal communication with the interior volume of the vessel, with said at least one thermowell being adapted for supply of a heat transfer fluid thereto for input of heat to the adsorbent material to effect desorption of adsorbed fluid therefrom.

15. The fluid storage and dispensing apparatus of claim 14, wherein the thermal management assembly comprises a monitoring and control assembly that is arranged to monitor pressure of fluid being dispensed from the vessel, and/or other process variable(s)/condition(s) of the dispensing, and to responsively and controllably actuate a pump or other fluid driver to circulate hot heat transfer fluid through the thermowell(s) and heat the adsorbent for desorption of adsorbed fluid therefrom.

16. The fluid storage and dispensing apparatus of claim 15, wherein the monitoring and control assembly is arranged so that when pressure of fluid being dispensed from the vessel reaches a lower control limit, the hot heat transfer fluid is pumped through the thermowell(s) to heat the adsorbent for desorption of adsorbed fluid therefrom.

17. The fluid storage and dispensing apparatus of claim 16, wherein the hot heat transfer fluid is controlled as to its specific temperature and/or flow rate.

18. The fluid storage and dispensing apparatus of claim 14, wherein said at least one thermowell comprises a thermowell arranged so that a distal portion thereof extends into the interior volume of the vessel and a proximal portion thereof is positioned exteriorly of the vessel with coupling structure accommodating engagement of the thermowell with flow circuitry for the heat transfer fluid.

19. The fluid storage and dispensing apparatus of claim 18, wherein the flow circuitry comprises a coaxial conduit.

20. A fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel with an interior volume holding an adsorbent material having sorptive affinity for a fluid to be stored on and desorptively dispensed therefrom, and at least one thermowell arranged for thermal communication with the interior volume of the vessel, with such at least one thermowell being adapted for supply of chemically-generated heat to the adsorbent material to effect desorption of adsorbed fluid therefrom.

21. The fluid storage and dispensing apparatus of claim 20, wherein chemical heat generation source material is disposed in the thermowell and arranged to be actuated to chemically generate heat for transfer from the thermowell to the vessel and adsorbent.

22. The fluid storage and dispensing apparatus of claim 21, wherein the chemical heat generation source material is arranged to be contacted with a co-reactant delivered to the thermowell at a controlled rate by a monitoring and control assembly that is arranged to introduce the co-reactant from a source of same in response to a monitored condition of the dispensing operation.

23. The fluid storage and dispensing apparatus of claim 22, wherein the co-reactant source comprises a pump that is modulated by the monitoring and control assembly in response to delivery pressure of fluid dispensed from the fluid storage and dispensing vessel.

24. The fluid storage and dispensing apparatus of claim 23, comprising a pressure transducer arranged to monitor said delivery pressure of fluid dispensed from the fluid storage and dispensing vessel.

25. The fluid storage and dispensing apparatus of claim 22 wherein the co-reactant source comprises a pressurized container holding gaseous co-reactant, with the pressurized container coupled to a co-reactant gas feed line having a flow control valve therein, and wherein the monitoring and control assembly is arranged to translate a valve element in the flow control valve between fully open and fully closed positions in response to sensing of dispensed fluid pressure, vapor pressure in the interior volume of the fluid supply and dispensing vessel, and/or other process condition(s) or variable(s) monitorable by the monitoring and control assembly to reflect the approach or occurrence of heels-limited capacity of fluid in the vessel.

26. The fluid storage and monitoring apparatus of claim 22, wherein chemical heat generated by the chemical heat generation source material is controlled by the monitoring and control assembly so that heels fluid is dispensed from the vessel at a predetermined rate and/or pressure.

27. The fluid storage and dispensing apparatus of claim 22, wherein the chemical heat generation source material is sodium metal, and the co-reactant is oxygen gas.

28. The fluid storage and dispensing apparatus of claim 27, wherein the chemical heat generation source material and co-reactant are separated from one another by a separation device or subassembly.

29. The fluid storage and dispensing apparatus of claim 27, wherein the monitoring and control assembly comprises a vapor pressure monitor arranged to monitor vapor pressure in the fluid storage and dispensing vessel, and to responsively contact the chemical heat generation source material with co-reactant when the monitored vapor pressure falls below a predetermined level.

30. The fluid storage and dispensing apparatus of claim 21, wherein the chemical heat generation source material comprises Na/K eutectic material.

31. A fluid storage and dispensing apparatus, comprising a fluid storage and dispensing vessel with an interior volume holding adsorbent having sorptive affinity for a fluid to be stored on and desorptively dispensed therefrom, and a vortex chiller that is arranged to be actuatable to provide heating of the adsorbent to enhance fluid desorption therefrom.

32. The fluid storage and dispensing apparatus of claim 31, wherein the vortex chiller is arranged for selective heating or cooling of the adsorbent.

33. The fluid storage and dispensing apparatus of claim 31, further comprising a chamber interior to or exterior of the fluid storage and dispensing vessel, and arranged to receive heated gas from the vortex chiller, for heating of the vessel and/or adsorbent.

34. The fluid storage and dispensing apparatus of claim 32, wherein the vortex chiller is arranged to chill the adsorbent during initial charging and subsequent storage of fluid on the adsorbent, and to heat the adsorbent during dispensing operation to enhance desorptive dispensing of heels fluid from the vessel.

35. The fluid storage and dispensing apparatus of claim 32, wherein the vortex chiller is coupled with (i) a source of compressed gas arranged for flow to an inlet of the vortex chiller, and (ii) flow circuitry receiving hot gas and cold gas outputs of the vortex chiller, with a diverter valve adjustably arranged to flow either hot gas or cold gas from the flow circuitry for said selective heating or cooling of the adsorbent.

36. The fluid storage and dispensing apparatus of claim 31, further comprising a monitoring and control assembly arranged to monitor pressure of fluid dispensed from the fluid storage and dispensing vessel, and to responsively modulate the vortex chiller to achieve a desired pressure level of the fluid dispensed from the fluid storage and dispensing vessel.

37. The fluid storage and dispensing apparatus of claim 36, wherein the monitoring and control assembly is non-electrical in character.

38. The fluid storage and dispensing apparatus of claim 36, wherein the monitoring and control assembly comprises a pneumatic monitoring and control assembly.

39. The fluid storage and dispensing apparatus of claim 31, wherein the vortex chiller is arranged to receive a carrier gas and to discharge heated carrier gas for flow through the interior volume of the fluid storage and dispensing vessel for contact with the adsorbent therein.

40. A fluid storage and dispensing apparatus comprising a fluid storage and dispensing vessel holding a storage medium for fluid on which fluid is stored and from which fluid is dispensed under dispensing conditions comprising thermal modulation of the storage medium, and a thermal management assembly arranged to thermally modulate the storage medium, wherein the thermal management assembly comprises at least one of a thermowell and a vortex chiller.

41. A method of increasing availability of dispensed fluid from a fluid storage and dispensing vessel holding adsorbent having fluid adsorbed thereon, comprising dispensing fluid from the vessel under dispensing conditions comprising desorption of fluid from the adsorbent, and providing a thermal input to the adsorbent to desorptively remove at least a portion of heels fluid from the adsorbent during a final portion of said dispensing.

42. The method of claim 41, wherein the final portion of said dispensing comprises dispensing when less than 40% by volume of fluid initially present in the vessel remains.

43. The method of claim 41, wherein the final portion of said dispensing comprises dispensing when less than 20% by volume of fluid initially present in the vessel remains.

44. The method of claim 41, wherein the final portion of said dispensing comprises dispensing when less than 10% by volume of fluid initially present in the vessel remains.

45. The method of claim 41, wherein the final portion of said dispensing comprises dispensing when less than 5% by volume of fluid initially present in the vessel remains.

46. The method of claim 41, wherein the thermal input is provided from a thermowell disposed in an interior volume of the fluid storage and dispensing vessel.

47. The method of claim 46, wherein the thermowell is in contact with at least a portion of said adsorbent.

48. The method of claim 41, wherein the thermal input is provided by an exothermic chemical reaction.

49. The method of claim 41, wherein the thermal input is provided by a vortex chiller.

50. A method of reducing heels fluid in dispensing of fluid from adsorbent on which the fluid is adsorptively stored and from which the fluid is desorbed for dispensing, said method comprising use of a fluid storage and dispensing apparatus according to any one of claims 1-40.