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WO2000050154A1 - Procede et dispositif d'adsorption modulee de la vapeur d'eau - Google Patents

Procede et dispositif d'adsorption modulee de la vapeur d'eau Download PDF

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Publication number
WO2000050154A1
WO2000050154A1 PCT/US2000/004081 US0004081W WO0050154A1 WO 2000050154 A1 WO2000050154 A1 WO 2000050154A1 US 0004081 W US0004081 W US 0004081W WO 0050154 A1 WO0050154 A1 WO 0050154A1
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Prior art keywords
gas stream
adsorbent material
recited
component
relative humidity
Prior art date
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PCT/US2000/004081
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English (en)
Inventor
Barry K. Speronello
Appadurai Thangaraj
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BASF Catalysts LLC
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Engelhard Corp
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Priority to AU34941/00A priority Critical patent/AU3494100A/en
Publication of WO2000050154A1 publication Critical patent/WO2000050154A1/fr
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Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/06—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/11—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/34—Specific shapes
    • B01D2253/342—Monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40001—Methods relating to additional, e.g. intermediate, treatment of process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds

Definitions

  • the present invention relates to a method for separating gaseous mixtures; and more particularly, to the use of humidity swing adsorption processes to separate such mixtures.
  • adsorption processes gas to be separated is fed through a bed of adsorbent material to extract the adsorbed component and produce a stream that is rich in the non- adsorbed component.
  • VOC's volatile organic compounds
  • Typical adsorption processes are based on thermal or pressure swing, purge gas stripping and displacement desorption. All of these however, have numerous drawbacks, making them suitable only for specific separation processes.
  • an adsorbent is used to selectively adsorb one constituent from a gas mixture at higher pressure to produce a gas stream that is depleted of the adsorbed constituent.
  • PSA pressure swing adsorption
  • a minimum of two adsorbent beds is used to maintain a steady flow of product gas so that at any time at least one bed is producing product gas while the other is undergoing regeneration.
  • Vacuum swing adsorption (“VS A”) processes such as disclosed in U S Patent No 5,015,271, and pressure/vacuum swing adsorption (“P/VSA”) processes such as disclosed in U S Patent No 5,702,504, both patents of which are expressly incorporated herein by reference, are subsets of PSA which utilize a lower pressure of less than 1 atmosphere for regeneration of the adsorbent bed
  • Equipment used in the PSA, NSA, and P/NSA process is expensive, requiring a multitude of pressure or vacuum vessels, compressors or vacuum pumps, valves to control the flow of the different gas streams to and from the adsorbent beds, as well as a large amount of adsorbent material
  • Substantial amounts of energy are needed to pressurize and repressurize or evacuate the adsorbent beds, causing large energy costs to
  • an adsorbent selectively adsorbs one constituent of a gas mixture at a lower temperature to produce a gas stream that is depleted of the adsorbed constituent
  • TSA thermal swing adsorption
  • TSA is usually conducted with two or more fixed beds of adsorbent material, one of which is producing product gas while the other is undergoing regeneration
  • the fixed bed arrangement is expensive, requiring multiple adsorbent vessels capable of withstanding the relatively high regeneration temperatures Numerous valves are needed to control the various gas flows to and from the adsorbent vessels, and expensive heating equipment is required to generate the high temperatures required for regeneration of the adsorbent beds
  • the TSA process uses a rotating monolithic bed which cycles the adsorbent between the lower temperature adsorption zone and the higher temperature desorption zone
  • the rotating bed arrangement is expensive as it requires a sophisticated structure to support the moving bed of adsorbent as it expands and shrinks due to thermal cycling
  • TSA also requires relatively high amounts of energy to heat the adsorbent material to the regeneration temperature, with the additional consequence that the heated regeneration purge stream dilutes the desorbed material
  • the process is further limited by the requirement that the temperature of the gas in the adsorption zone be kept relatively low Any increase in
  • Additional adsorption processes include purge gas stripping and displacement adsorption
  • purge gas stripping an adsorbent bed is regenerated at constant pressure and temperature by purging with a non-adsorbing inert gas This process is only useful for weakly held adsorbed species, owing to the large, and hence, expensive, amount of purge gas otherwise required
  • Displacement desorption is similar to purge gas stripping, but instead of utilizing an inert purge, the adsorbed species are displaced by a stream containing a competitively adsorbed species In such processes however, product recovery becomes complex and expensive due to product contamination by the displacing agent Additionally, the choice of the adsorbent material is critical
  • displacement desorption uses water as a displacing agent, but in all cases the adsorbent requires a subsequent high temperature thermal treatment to desorb the water from the adsorbent or, alternatively, regenerate the adsorbent See, for example, U S Patent Nos 4,966,611 and 4,319,
  • the present invention provides a method for separating gaseous mixtures comprising (a) contacting a feed gas stream containing at least two components with an adsorbent material to adsorb at least one component from the feed gas stream to produce a depleted gas stream diminished in the adsorbed component and a loaded adsorbent material, and (b) contacting a desorption gas stream with the loaded adsorbent material to desorb the adsorbed component therein and produce an enriched gas stream containing a desorbed component and a regenerated adsorbent material depleted of the adsorbed component wherein the regenerated adsorbent material is suitable for reuse in step (a) and wherein the relative humidity of the desorption gas stream is higher than the relative humidity of the feed gas stream
  • the adsorbent material does not have to be thermally regenerated before reuse and in that way, significantly differs from the prior art
  • the temperature of the feed gas and desorption gas streams need not be controlled so long as the relative humidity of the desorption gas stream is higher than the feed gas stream
  • the temperature of the feed gas stream may be greater than the temperature of the desorption gas stream so long as the relative humidity of the desorption gas stream is higher than that of the feed gas stream
  • the method of the invention can separate gaseous mixtures in which the component to be adsorbed is less polar than at least one of the remaining constituents of the gaseous mixture
  • the separation of gaseous hydrocarbon-water containing mixtures less polar hydrocarbons will be adsorbed onto the adsorbent material instead of the more polar water molecules
  • the method described and claimed herein can effectively separate gaseous components without additional processing requirements or costly equipment It is far less expensive to operate than the prior art separation processes Additionally, the method of the present invention may be readily adapted to numerous process steams, making it ideally suited for a wide variety of applications Advantageously, a single separation scheme may be used in a large industrial processing plant in which a number of different streams require separation The method of the present invention is also useful in small scale applications such as solvent vapor recovery from dry cleaning establishments
  • FIG. 1 is a schematic representation depicting a fixed two bed apparatus in which each bed is alternately contacted by the lower humidity feed gas stream and the higher humidity desorption gas stream in accordance with the present invention
  • FIG.2 is a diagrammatic perspective view depicting an adsorbent-coated rotating honeycomb wheel which cycles between the lower humidity feed gas stream and the higher humidity desorption gas stream in accordance with the present invention
  • FIG. 3 is a graph depicting the carbon content of the adsorbent material as a function of relative humidity, the graph illustrates that volatile organic compounds adsorb onto adsorbent material at low humidity conditions and desorb from the adsorbent material at high humidity conditions
  • FIG. 4 is a graph depicting the carbon content of the adsorbent material as a function of temperature, the graph illustrates that adsorption of acetaldehyde and formaldehyde at low relative humidity is relatively temperature insensitive, and
  • FIG. 5 is a graph depicting outlet hydrocarbon concentration from a bed of adsorbent material as a function of time during the adsorption and desorption steps of the present invention
  • the present invention is an improved method for separating gaseous mixtures comprising an adsorption step at a lower relative humidity and a desorption step at a higher relative humidity in which the higher humidity condition causes desorption of the adsorbed phase from the adsorbent material and in that way regenerates the adsorbent
  • the method of the present invention comprises (a) contacting a feed gas stream containing at least two components with an adsorbent material to adsorb at least one component from the gas stream to produce a depleted gas stream diminished in the adsorbed component and a loaded adsorbent material, and (b) contacting a desorption gas stream with the loaded adsorbent material to desorb the adsorbed component therein and produce an enriched gas stream containing a desorbed component and a regenerated adsorbent material depleted in the adsorbed component wherein the regenerated adsorbent material is suitable for reuse in step (a) and wherein the relative humidity of the desorption gas stream is higher than the relative humidity of the feed gas stream
  • FIG 1 of the drawings there is shown a schematic view of a fixed two bed adsorption system 10 comprised of adsorption beds A and B, each of which is packed with adsorb
  • a feed gas stream comprising air and minor amounts of at least one hydrocarbon component is introduced into the system of FIG 1 through inlet line 13 which, on its downstream end, is joined to inlet gas manifold 14
  • Manifold 14 is connected to adsorbent bed inlet lines 15a and 15b, which are, in turn, connected to the inlet ends of adsorbent beds A and B, respectively
  • the gas outlet ends of adsorbent beds A and B are connected to adsorbent bed outlet lines 16 and 16b, respectively
  • High humidity gas inlet line 17 is connected on its downstream end to inlet gas manifold 18
  • Manifold 18 is connected to adsorbent bed inlet lines 19a and 19b, which are, in turn, connected to the inlet ends of adsorbent beds A and B, respectively
  • Flow between manifold 14 and inlet line 15 ⁇ and manifold 14 and inlet line 15b is controlled by valves 20a and 20b, respectively, which are located in inlet lines 15 ⁇ and 15 b, respectively
  • valves 20 ⁇ and 21b are open and all other valves (21 ⁇ and 20b) are closed
  • the process is conducted at atmospheric pressure, although pressures of from about 0 01 atmospheres to about 100 atmospheres are within the scope of the present invention
  • the feed gas stream When the feed gas stream is introduced into the system via line 13, it flows through manifold 14 and enters adsorbent bed A via inlet line 15a
  • This feed gas stream should have a relative humidity that is from 0 to about 80%, preferably from 0% to about 50%, and most preferably from 0 to about 30%
  • relative humidity it is meant the ratio of actual water vapor pressure of the gas stream to the saturation water vapor pressure, expressed as a percentage
  • the feed gas stream has a temperature range of from room temperature to about 250 °C where hydrocarbon components are to be separated That at least one component from the feed gas can be readily adsorbed onto the adsorbent material ⁇ 2a at a high temperature is particularly surprising in light of the generally accepted knowledge in the art that high temperature causes desorption of hydrocarbons from an adsorbent material
  • the feed gas stream can be dried or heated slightly to reduce its relative humidity
  • the feed gas stream may be heated to a temperature of from about 35 °C to about 250°C Such heating of the feed gas stream
  • a loaded adsorbent material can contain at least a minor amount of adsorbable components
  • a loaded adsorbent material can contain from about 0 1 weight % to about 80 weight % of the adsorbable component, and typically from about 2 weight % to about 50 weight % of the adsorbable component
  • the adsorbent material can, but need not adsorb, 100% of the at least one hydrocarbon component from the feed gas Accordingly, the adsorbent material can adsorb and separate even trivial amounts of the at least one hydrocarbon component from the feed gas
  • the adsorbent material will adsorb from about 25 weight % to about 100 weight %, and more typically, 50 weight % to about 99 weight % of the at least one hydrocarbon component from the feed
  • feed gas continues to be pumped through adsorbent bed A until the pores of adsorbent material ⁇ 2a are sufficiently loaded with the at least one hydrocarbon component such that the hydrocarbon concentration of the depleted gas stream leaving through outlet line 16a is increased from its initial value
  • adsorbent bed B undergoes desorption/ regeneration This is accomplished by passing a desorption gas stream having a relative humidity which is higher than the relative humidity of the feed gas stream via high humidity gas inlet line 17 through manifold 18 and inlet line 21b into adsorption bed B
  • High levels of relative humidity may be simply and inexpensively produced by fiinneling the gas stream through a water saturated monolithic structure (not shown) prior to entry into manifold 18
  • Such devices are often referred to as evaporator pads and are conventionally used to cool and humidify interior environmental air in dry geographic regions These devices, which are generally known as " Swamp Coolers, " are attractive because they are inexpensive, contain few moving parts and do not require additional energy to operate
  • the relative humidity of the desorption gas stream entering adsorption bed B should be as high as possible to maximize displacement of the at least one hydrocarbon component from the adsorbent material 12b
  • the relative humidity of the desorption gas stream is from greater than about 0% to about 100%, more preferably, from about 30% to
  • the temperature of the desorption gas stream need not be controlled as long as the relative humidity is higher than that of the feed gas stream
  • the adsorption and desorption/regeneration steps may occur under different temperature conditions as, for example, where the temperature of the feed gas stream is higher than the temperature of the desorption gas stream
  • Typical temperature ranges of the desorption gas stream is from about 0°C to about 250 °C and typically from about 0°C to about 100°C
  • the present invention is completely opposite than the TSA processes of the prior art
  • the desorption gas stream functions to desorb at least a minor amount of the at least one adsorbed hydrocarbon component from the adsorbent material
  • the at least one hydrocarbon component is desorbed from adsorbent material 12b, it exits adsorbent bed B via outlet line 16b to form a gas stream enriched in the hydrocarbon component, hereinafter the enriched gas stream
  • this enriched gas stream will contain from about 0 01 mole % to about 100 mole % of the at least one hydro
  • adsorbent material 12b is not dried at a high temperature, and as such, specifically differs from high temperature drying of water saturated adsorbent material which is required by, for example, A A Seballo, et al , Low-Temperature Displacement Desorption of Substances Adsorbed on NaX Zeolite, Journal of Applied Chemistry of the USSR, Vol 43, No 1 1, pp 2439-43 (Nov 1970)
  • high temperature drying is meant heating the regenerated adsorbent material to a temperature exceeding 250°C to prepare the adsorbent material for the next adsorption cycle
  • the regenerated adsorbent bed may be void of all of the at least one hydrocarbon component or, alternatively, it may have only slightly less of the at least one hydrocarbon component than the loaded adsorbed material discussed previously with reference to adsorbent bed A, or it may contain any range of hydrocarbon concentration therein Typically, the regenerated adsorbent bed will contain from about 0 weight % to about 79 weight % and more typically, from about 0 1 weight % to about 49 weight % of at least one hydrocarbon component
  • the humidity swing process described herein does not require high temperatures to effectively desorb/regenerate the adsorbent material
  • extra water would be added by an evaporator pad, mist or the like
  • the desorption gas stream entering adsorbent bed B comprises substantially 100% water vapor at 100° C and 1 atmosphere pressure (i e , it is saturated steam)
  • warm desorption gas contains a higher concentration of water vapor
  • the first half-cycle is terminated and the second half-cycle is begun At this point, valves 21 and 20b are opened and all other valves are closed
  • the second half of the cycle is identical to the first half of the cycle except that the phases conducted in adsorbent beds A and B are reversed, such that in the second half-cycle, adsorbent bed B is in the adsorption phase and adsorbent bed A is in the desorption/regeneration phase, as described above
  • the adsorbent material may be contacted with relatively dry gas at a temperature not exceeding about 250 °C to at least partially desorb some of the adsorbed water vapor from the adsorbent material and better prepare the adsorbent material for the next adsorption cycle
  • FIG 2 illustrates a preferred embodiment of the present invention 30 wherein the adsorbent material is contained in a rotating monolithic bed which alternately contacts the lower and higher humidity gas streams
  • This type of configuration is particularly suitable for use in open-cycle air conditioning systems, such as described in U S Patent No 4,594,860, the entirety of which is incorporated herein by reference
  • the outer enclosure of the device shown in FIG 2 has been omitted so the internal working parts may be shown more clearly
  • the adsorbent-coated wheel 35 is constructed of a plurality of adjoining parallel channels which are generally hexagonal in shape, such as described in U S Patent No 5,733,451, the entire disclosure of which is expressly incorporated herein by reference
  • the material used to construct the adjoining parallel channels comprise a non- metallic, high- strength, temperature-resistant, low thermal conductivity material such as Nomex ® aramid in paper form, commercially available as 0 55 Hexagonal Core honeycomb from Engelhard/Hex Core, L L P , Iselin, N J
  • the hexagonal honeycomb is coated with the adsorbent material by methods which are well known and readily available to the skilled artisan This adsorbent-coated material interacts with the feed or desorption gas streams to achieve adsorption or desorption as necessary
  • a "gaseous mixture" which may be separated in accordance with the method taught herein refers to any stream which contains at least two components in the gaseous phase and may comprise two, three, four and more components
  • the method of the present invention can separate hydrocarbon laden mixtures containing olefmic and paraffinic components or fermentation mixtures, it may be used to purify chemical mixtures, or it may be used to recover carbon dioxide, sulfur dioxide or a mixture of different gases from a multi component gas stream
  • the method described herein is effective for separating styrene from flue gas and VOC's such as acetylaldehyde and/or formaldehyde from indoor air Due to the many different gaseous mixtures which may be separated, it is contemplated that the feed gas stream may contain any combination of components to be separated
  • VOC's such as acetylaldehyde and/or formaldehyde
  • Selectivity of the adsorbent material for a particular adsorbable component is generally governed by the volume and distribution of the pore size in the adsorbent material Gaseous molecules having a kinetic diameter less than, or equal to, the pore size of the adsorbent material can enter the intracrystalline void space in the adsorbent material while molecules having a diameter larger than the pore size of the adsorbent are excluded from and not retained by the pores of the adsorbent material
  • the adsorbent material thus can sieve gaseous molecules according to their molecular size
  • the kinetic diameters of various molecules are provided in D W Breck, Zeolitic Molecular Sieves, John Wiley and Sons (1974), p 636
  • the adsorbent material may also separate molecules according to their different rates of diffusion in the pores of the adsorbent material
  • the specificity shown by an adsorbent material towards an adsorbed component may also be influenced by the electrostatic charge of the adsorb
  • activated carbons, activated alumina and silica gel have pores which are non-uniformly sized Consequently, many different gaseous molecules can enter the pores of these compounds
  • most zeolitic materials have uniformly sized pores of about 3 Angstroms to about 10 Angstroms, making these materials well suited to adsorb only those gaseous molecules which are smaller than the pore size of the particular zeolitic material Accordingly, these materials are particularly useful in the practice of this invention
  • a large-pored crystalline titanium silicate molecular sieve zeolite as claimed in U S Patent No 4,853,202, the entire disclosure of which is incorporated herein by reference, in its substantially hydrogen ion exchanged form is particularly preferred
  • Methods for ion-exchanging molecular sieve materials such as zeolites to obtain, for example, a hydrogen ion exchanged form are well known and readily available to the skilled artisan
  • the quantity of gas that is adsorbed by the adsorbent material depends on the pressure, temperature, and the nature of the gas and the adsorbent material Any gas which is capable of adsorbing on a surface may be separated by the method described and claimed herein Thus, noble gases and other weakly adsorbed species are not particularly suitable in the practice of the present invention
  • a gaseous mixture containing several components adsorbed by a single adsorbent material may be removed from the feed gas at a single time
  • several components may be adsorbed by sequentially contacting the feed gas with a series of different adsorbent materials, each of which is selective for a different gaseous molecule (i e , the adsorption step of the process may be repeated one or more times prior to beginning the desorption step of the process)
  • Each of the feed and desorption gas streams may contact the adsorbent one or more times
  • the feed gas stream might contact several different adsorbent materials, each of which is selective for adsorbing a different species contained in the feed gas such that only a single desired constituent remains unadsorbed
  • the number of times the process may be repeated is almost limitless
  • the gas stream exiting the adsorbent material may be recovered for use in another process stream, or alternatively, it may be recycled in the method described herein as the desorption gas stream such as, for example, where a single component is stripped from an air stream In this instance, some or all of the resultant stripped air stream may be humidified and used as the desorption gas stream
  • the gas stream exiting the adsorbent material may be a purified product gas, a stream of waste gas material in which the adsorbed component is recovered, a multi-component gaseous mixture diminished in a single adsorbed component, or the like
  • the method described and claimed herein may be applied to any number of process streams in which at least one component is to be separated
  • the method described herein may be adapted to small scale process streams such as recovery of solvent vapors from dry cleaning establishments, or to large industrial process streams such as flue gas clean-up, chemical purification, separation of azeotropic mixtures, and the like
  • the method of the present invention can separate even very minute quantities (vppm) of components from a gaseous stream without the use of high temperature or pressure apparatuses
  • vppm very minute quantities
  • This Example illustrates the separation of acetaldehyde from a gaseous water stream by humidity swing adsorption under static conditions
  • FIG 3 demonstrates that at room temperature and a RH of 30%, the adsorbent material can adsorb sufficient AcA to correspond to about 2 5 weight percent carbon Upon exposure to 80% RH and room temperature conditions, approximately 50% (1 2 weight percent) of the carbon will desorb from the adsorbent material At 100% RH and room temperature conditions, about 80% (2 0 weight percent) of the AcA will desorb from the adsorbent material This provides a humidity swing adsorption capacity of between about 1 5% and 2 5%, depending upon the desorption RH
  • FIG 4 demonstrates that the adsorption capacity of the adsorbent material for AcA at low RH is relatively insensitive to temperature up to about 190°F
  • Example 2 This Example illustrates the separation of VOC's other than AcA from a gaseous water stream by humidity swing adsorption under static conditions
  • FIG 3 One gram samples of the FA laden adsorbent material were additionally placed in aluminum foil pans in a preheated oven at either 140°F or 190°F and between about 1% and about 4% RH for 30 minutes After this heat treatment, the carbon content of the samples was measured with a LECO carbon analyzer
  • Example 3 This Example details the preparation of an adsorbent material for use in the humidity swing method
  • This honeycomb core material had a wall thickness of about 0 0015 inches and a channel diameter of about 0 055 inches From this honeycomb were cut small pieces having a square cross section (i e , perpendicular to the direction of the channels) of about 0 6 inches on a side and having a length (parallel to the direction of the channels) of about 1 5 inches
  • HETS-10 was obtained from an Engelhard Corporation manufacturing facility as a 40% solid aqueous slurry containing 2% by weight of latex binder solids (Nacrylic brand 4260, available from National Starch Company, Bridgewater, N J )
  • An equivalent slurry may be prepared using the method given in the paragraph below, but substituting HETS-10 powder for ammonium Y powder
  • the other adsorbent material was ammonium Y powder ("NH 4 Y”) obtained from an Engelhard Corporation manufacturing plant in Savannah, GA , substantially equivalent to Molecular Sieve Catalyst support-ammonium Y zeolite powder (Cat No 33,4413-3), Aldrich Chemical Co , Milwaukee, WI
  • An aqueous slurry was prepared from the ammonium Y powder by adding 158 grams of the powder to 222 grams of deionized water and mixing with a spatula until the slurry was uniform
  • the honeycomb samples were coated with the different adsorbents as follows
  • honeycomb piece was weighed, oriented with its channels in the vertical direction and immersed into the coating slurry 3 The immersed honeycomb piece was held under the surface of the coating slurry and gently agitated up and down until no additional bubbles come to the surface of the coating slurry
  • honeycomb piece was raised to remove it from the slurry with the honeycomb channels still oriented in the vertical direction, and excess coating slurry was allowed to drain from the honeycomb channels
  • step (6) If a sufficient weight of adsorbent coating was achieved, the honeycomb piece was dried for 2 hours at about 100°C and weighed If a sufficient weight of adsorbent coating was not achieved after step (6), then steps (1) through (6) were repeated on the partially coated honeycomb piece until the target coating weight was reached
  • This Example illustrates the separation of VOC's by a dynamic humidity swing adsorption system.
  • An adsorbent coated honeycomb piece, prepared as described in Example 3 was wrapped with ceramic fiber blanket and inserted into a 2.5 centimeter diameter adsorber tube made of fused silica. The ceramic fiber material was gently compressed between the honeycomb piece and the inner wall of the adsorber tube to provide a sufficiently gas tight seal so that substantially all of the gas flow was through the channels of the honeycomb pieces.
  • Air at 30°C and either ⁇ 1% or 50% RH was passed through the adsorber tube containing the adsorbent coated honeycomb piece at a rate sufficient to produce a space velocity of 22,500 hr "1 as determined by the equation: (Volume Air @ STP)/(Volume of Coated Honeycomb Piece/Hr). This space velocity was maintained for 30 minutes. At that time to begin the adsorption step of the process, VOC vapor was added to each of the ⁇ 1% and 50% RH air streams at a concentration of nominally 50 vppm (parts per million by volume) (methane equivalents).
  • VOC concentration entering and leaving the adsorber tube was measured using a flame ionization detector hydrocarbon analyzer (Rosemont Analytical Model 400 A). This continued until the VOC concentrations entering and exiting the adsorber tube were equal (i.e., the adsorbent was loaded with VOC). At that time, the VOC concentration of the gas entering the adsorber tube was reduced to zero and the RH was increased to 100% until the VOC concentration leaving the adsorber tube fell to zero. The temperature during the desorption phase was 30 °C. These procedures were repeated four times to authenticate the results.
  • FIG 5 depicts the outlet hydrocarbon concentration from the adsorber tube as a function of time using a HETS-10 coated honeycomb piece and acetaldehyde (“AcA") as the VOC
  • the RH of the air prior to and during the adsorption step was 50% Time zero (0) was defined as the time when the VOC was first introduced into the inlet of the adsorber tube
  • Data from the adsorption step of the humidity swing adsorption cycle is shown as unfilled squares, and it is scaled to the Y axis scale on the left side of the graph (0-50 vppm)
  • Data from the desorption step of the cycle is shown as filled squares, and it is scaled to the Y axis scale on the right side of the graph 0-1000 vppm)
  • FIG 5 illustrates that substantially all of the AcA was removed from the air stream by the adsorbent material during the first 2 hours of adsorption The VOC exiting the adsorbent material was less than 10% (less than 4 4
  • Example 3 is set forth in Table 2 For each combination of adsorbent material and VOC,
  • Table 2 reports the duration of complete VOC removal, the duration of >90% VOC removal, the time needed to saturate the adsorbent, the time to achieve peak outlet VOC concentration during desorption, the peak VOC concentration during desorption, and the time to complete desorption Table 2
  • Table 2 demonstrates that the humidity swing adsorption process can operate with different adsorbent material/adsorbed gas combinations
  • adsorbents such as silica- alumina gel, titania-silica gel and zeolitic molecular sieves such as types L, Beta, X, chabazite, clinoptililite, etc are also suitable for the humidity swing process
  • the adsorbed gas need not be a VOC, but may be any other gas which is capable of being adsorbed
  • the desorption step was conducted at the same temperature as the adsorption step, the two steps may be conducted at different temperatures as long as the relative humidity of the desorption gas is higher than the adsorption gas

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Ce procédé de séparation d'au moins un constituant à partir d'un mélange gazeux comprend les étapes suivantes consistant : (a) à mettre en contact un courant gazeux d'alimentation contenant au moins deux constituants, avec un matériau adsorbant, de manière à adsorber au moins l'un de ces constituants, à partir du courant gazeux, et produire un courant gazeux appauvri en constituant adsorbé, ainsi qu'un matériau adsorbant chargé, et (b) à mettre en contact un courant gazeux de désorption avec le matériau adsorbant chargé, afin de désorber le constituant adsorbé par le matériau et produire un courant gazeux enrichi contenant un constituant désorbé et un matériau adsorbant régénéré, appauvri en constituant adsorbé. Ce processus est en outre caractérisé en ce que le matériau adsorbant régénéré est approprié à une réutilisation dans l'étape (a), et en ce que l'humidité relative du courant gazeux de désorption est supérieure à l'humidité relative du courant gazeux d'alimentation. Les constituants gazeux sont utilement séparés de manière efficace et économique. Ce procédé de séparation est notamment conçu pour accepter de nombreux courants de traitement et des utilisations relativement différentes. Ainsi, ce procédé est utile dans de grandes installations de traitement industriel, de même que dans des applications à petite échelle. L'invention concerne également un dispositif de séparation des constituants gazeux.
PCT/US2000/004081 1999-02-22 2000-02-17 Procede et dispositif d'adsorption modulee de la vapeur d'eau Ceased WO2000050154A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU34941/00A AU3494100A (en) 1999-02-22 2000-02-17 Humidity swing adsorption process and apparatus

Applications Claiming Priority (2)

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US25553999A 1999-02-22 1999-02-22
US09/255,539 1999-02-22

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WO2000050154A1 true WO2000050154A1 (fr) 2000-08-31

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
WO2009061836A1 (fr) * 2007-11-05 2009-05-14 Global Research Technologies, Llc Elimination de dioxyde de carbone contenu dans de l'air
US7993432B2 (en) 2006-03-08 2011-08-09 Kilimanjaro Energy, Inc. Air collector with functionalized ion exchange membrane for capturing ambient CO2
US8999279B2 (en) 2008-06-04 2015-04-07 Carbon Sink, Inc. Laminar flow air collector with solid sorbent materials for capturing ambient CO2
US9266052B2 (en) 2006-10-02 2016-02-23 Carbon Sink, Inc. Method and apparatus for extracting carbon dioxide from air
US9266051B2 (en) 2005-07-28 2016-02-23 Carbon Sink, Inc. Removal of carbon dioxide from air
US9527747B2 (en) 2008-02-19 2016-12-27 Carbon Sink, Inc. Extraction and sequestration of carbon dioxide
US9616375B2 (en) 2007-04-17 2017-04-11 Carbon Sink, Inc. Capture of carbon dioxide (CO2) from air
US11737398B2 (en) 2018-02-16 2023-08-29 Carbon Sink, Inc. Fluidized bed extractors for capture of CO2 from ambient air

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GB1008335A (en) * 1963-03-25 1965-10-27 Exxon Research Engineering Co Two-stage adsorption process
DE3423169A1 (de) * 1983-06-24 1985-01-10 Magyar Asványolaj és Földgáz Kisérleti Intézet, Veszprém Verfahren zur gewinnung von organischen substanzen aus gasen durch adsorption
US5198001A (en) * 1991-09-13 1993-03-30 Calgon Carbon Corporation Apparatus and process for removing organic compounds from a gas stream
US5542965A (en) * 1993-11-18 1996-08-06 U.E. Sebald Druck Und Verlag Gmbh Process and installation for removing solvent vapor from exhaust air

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
GB1008335A (en) * 1963-03-25 1965-10-27 Exxon Research Engineering Co Two-stage adsorption process
DE3423169A1 (de) * 1983-06-24 1985-01-10 Magyar Asványolaj és Földgáz Kisérleti Intézet, Veszprém Verfahren zur gewinnung von organischen substanzen aus gasen durch adsorption
US5198001A (en) * 1991-09-13 1993-03-30 Calgon Carbon Corporation Apparatus and process for removing organic compounds from a gas stream
US5542965A (en) * 1993-11-18 1996-08-06 U.E. Sebald Druck Und Verlag Gmbh Process and installation for removing solvent vapor from exhaust air

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9266051B2 (en) 2005-07-28 2016-02-23 Carbon Sink, Inc. Removal of carbon dioxide from air
US10010829B2 (en) 2005-07-28 2018-07-03 Carbon Sink, Inc. Removal of carbon dioxide from air
US7993432B2 (en) 2006-03-08 2011-08-09 Kilimanjaro Energy, Inc. Air collector with functionalized ion exchange membrane for capturing ambient CO2
US9205372B2 (en) 2006-03-08 2015-12-08 Carbon Sink, Inc. Air collector with functionalized ion exchange membrane for capturing ambient CO2
US10150112B2 (en) 2006-03-08 2018-12-11 Carbon Sink, Inc. Air collector with functionalized ion exchange membrane for capturing ambient CO2
US9266052B2 (en) 2006-10-02 2016-02-23 Carbon Sink, Inc. Method and apparatus for extracting carbon dioxide from air
US9861933B2 (en) 2006-10-02 2018-01-09 Carbon Sink, Inc. Method and apparatus for extracting carbon dioxide from air
US9616375B2 (en) 2007-04-17 2017-04-11 Carbon Sink, Inc. Capture of carbon dioxide (CO2) from air
WO2009061836A1 (fr) * 2007-11-05 2009-05-14 Global Research Technologies, Llc Elimination de dioxyde de carbone contenu dans de l'air
US9527747B2 (en) 2008-02-19 2016-12-27 Carbon Sink, Inc. Extraction and sequestration of carbon dioxide
US8999279B2 (en) 2008-06-04 2015-04-07 Carbon Sink, Inc. Laminar flow air collector with solid sorbent materials for capturing ambient CO2
US11737398B2 (en) 2018-02-16 2023-08-29 Carbon Sink, Inc. Fluidized bed extractors for capture of CO2 from ambient air

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