WO2006025557A1 - Dispositif pour épurer et concentrer un composé et procédé pour épurer et concentrer un composé à l’aide du dispositif - Google Patents

Dispositif pour épurer et concentrer un composé et procédé pour épurer et concentrer un composé à l’aide du dispositif Download PDF

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Publication number
WO2006025557A1
WO2006025557A1 PCT/JP2005/016175 JP2005016175W WO2006025557A1 WO 2006025557 A1 WO2006025557 A1 WO 2006025557A1 JP 2005016175 W JP2005016175 W JP 2005016175W WO 2006025557 A1 WO2006025557 A1 WO 2006025557A1
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WO
WIPO (PCT)
Prior art keywords
compound
fluid
concentration device
purification
gas
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Ceased
Application number
PCT/JP2005/016175
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English (en)
Inventor
Yoshio Fujiwara
Akiko Shinoda
Yoshihiro Ohki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
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Showa Denko KK
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Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of WO2006025557A1 publication Critical patent/WO2006025557A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01D53/0446—Means for feeding or distributing gases
    • 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
    • B01D2253/104—Alumina
    • 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
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • 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
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • 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
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings

Definitions

  • the present invention relates to a device for purifying and/or concentrating a compound (in Claims and Specification of the present invention, "purifying and/or concentrating” is simply denoted as “purifying and concentrating”) , and a method for purifying and concentrating the compound using the same.
  • porous particles which are excellent in an adsorption-desorption property have been developed and these porous particles have been provided in a market from a plurality of manufacturers as adsorbents for the solid phase extraction.
  • adsorbents for the solid phase extraction there are various shapes of articles such as a silica gel particle into which a functional group is introduced, apolymer particle such as a styrene-divinyl benzene copolymer, a carbonaceous particle such as activated carbon or carbon graphite and further, in recent years, activated carbon fiber prepared by sintering various types of synthetic fibers and a subsequent activating treatment or a rod-like porous continuous body (monolith) formed by polymerization in a column (bulk polymerization in the presence of a diluent) .
  • An appropriate article can be selected in accordance with applications.
  • An object of the invention is toprovide a compound concentration device which is characterized in that, while maintainingahighcapacityofpurifyingandseparatinga compound, pressure to be generated at the time of gas-passing or liquid-passing is relatively low and a clogging less occurs even in a case of a sample having many suspended solids; and a purification-concentration method using the device.
  • the present inventors have exerted intensive studies on a methodforproducinga compoundpurification-concentrationdevice which is characterized in that, while maintaining a high capacity of purifying and separating a compound, a pressure loss to be generated at the time of gas-passing or liquid-passing is relatively low and a clogging less occurs even in a case of a sample having many suspended solids.
  • the present inventors have found out that the object can be attained by not improving the packing material but improving a structure of the compound concentrationdevice, totherebyaccomplishthepresent invention.
  • the present invention relates to a compound purification-concentration device and a method for purifying and concentrating a compound as follows :
  • Acompoundpurification-concentrationdevice whichhas a packing material for purifying and concentrating a compound and a fluid permeating plate for holding the packing material at each end surface of the packingmaterial in a container having an inflow port and an outflow port for a fluid, being characterizedby having a space portion at an outer surface of the fluid permeating plate at each end surface of the packing material.
  • the compound purification-concentration device as described in 1 above comprising a projected structure for holding the fluidpermeatingplate on an inner side surface of the container at the outer surface side of at least one fluid permeating plate.
  • the compound purification-concentration device as described in 4 above, wherein the material which does not affect the purification-concentration of the compound comprises one or moremembers selectedfromthegroupconsistingofaglassparticle, aglass fiber, aquartzparticle, aquartz fiber, aceramicparticle, ametallicparticle, ametallic fiber, apolymerparticle, apolymer fiber, gravel and sintered articles thereof.
  • the compound purification-concentration device as described in any one of 1 to 14 above being designed such that when the fluid is a gas and is flown at a flow rate of 6 to 12 L/min, a linear velocity of the gas which passes through a side face of an imaginary column formed by a plane which is vertically dropped from a peripheral line of the inflow port or the outflow port of the fluid to the surface of the fluid permeating plate is to be 30 m/sec or less.
  • a method for purifying and concentrating a compound contained in a fluid being characterized by using the compound purification-concentration device as described in any one of 1 to 15 above.
  • a method for purifying and concentrating a compound inagas sample wherein the gas sample is flownbyusingthe compound purification-concentration device as described in any one of 1 to 15 above at a flow rate of 6 to 12 L/min such that a linear velocity is to be 30 m/sec or less when the gas passes through a side face of an imaginary column formed by a plane which is vertically dropped from a peripheral line of the inflow port or the outflowport of the fluid to the surface of the fluidpermeating plate.
  • FIG. 1 is a schematic diagram of a compound purification-concentration device having a tapered structure which is an example of the compound purification-concentration device according to the present invention.
  • FIG. 2 is a schematic diagram of the compound purification-concentration device of Comparative Examples.
  • FIG. 3 is a side view (A) and a plan view (B) schematically showing a compound purification-concentration device having a groove-like structure which is an example of the compound purification-concentration device according to the present invention.
  • FIG. 4 is an explanatory diagram of an imaginary column.
  • FIG. 1 contains, inside a container (1) having an inflow port (5) and an outflow port (6) of a fluid, a packing material (4) for purifying or concentrating a compound to be measured or a useful compound contained in the fluid and fluid permeating plates (3a, 3b) for holding the packing material at both end surfaces of the packing material, is characterized in that space portions (7a, 7b) are provided at outer surface sides of the both fluid permeating plates (3a, 3b) , respectively.
  • the fluid permeating plates (3a, 3b) which have permeation pores (not shown) all over the plates are set so as that the fluid can be dispersed all over the packing material (4) and also the packing material (4) is prevented from being leaked from inside the container (1) .
  • the fluidpermeatingplate for example, an article having a thickness of about 0.5 to about 3 mm formed by sintering polyethylene particles or a filter made of paper or glass fiber can be used.
  • projected structures may be provided on an inside surface of the container at the outer surface side of at least one fluidpermeatingplate.
  • Theprojected structures may be provided on the entire circumference or a part of the circumference so longas it holds stablythe fluidpermeating plates. By the projected structures, the fluid permeating plate can easily be held.
  • one method for providing the space portions (7a, 7b) is a method to provide a tapered structure (2) on an inside wall of the container at the outer surface side of the fluid permeating plate.
  • a taper angle ( ⁇ ) of the tapered structure is preferably 5 to 85°.
  • the angle is unduly small (when ⁇ is unduly large)
  • the fluid permeating plate is moved and the space portionis narrowed, orthepackingmaterialmayleakbydeformation or inclination of the fluid permeating plate.
  • a material which does not affect the purification-concentration of the compound is packed at the outer sides of the fluid permeating plates (3a, 3b) .
  • Such materials are, for example, glass, quartz, ceramics, metals and polymers.
  • Shapes thereof are not particularly limited and include a particle shape, a fiber shape, a sintered shape, a non-woven shape, but it is necessary that a surface structure thereof does not affect the intended purification-concentration of the compound to a great extent.
  • a particle diameter, a fiber diameter or void structure size of the material is unduly large, a uniformdispersion to the fluidpermeatingplate is hindered, which is not favorable; whereas, when it is unduly small, the material itself obstructs the flow of the fluid, which is not favorable.
  • still another method is a method to provide a groove-like structure on the outer sides of the fluid permeating plate.
  • the shape of the groove is not particularly limited so long as it forms a structure such that the fluid is allowed to be scattered all over the fluid permeating plate. An unduly complicated structure generates a large pressure loss as the fluid flow rate is increased, which is not favorable.
  • a groove-like structure As a side view and a plan view are shown in FIGS. 3(A) and 3(B), a groove-like structure (9) is preferred wherein projected structures (8) extend radially from the centers of an inflow port (5) and an outflow port (6) ofthe fluidto thewall.
  • the groove-like structure maybeprovided on the fluid permeating plate or an inner wall of the container. Further, aseparatelyformedarticlehavingagroove-likestructure may be provided.
  • Width of the groove can be changed depending on a size of the container or a number of grooves, for example, the width of one groove can be defined as 33.3% or less of a length of a circumference of a concentric circle to the point and a total width of the all grooves can be defined as 50 to 99% of a length of a circumference of a concentric circle to the point.
  • depth of the groove can be changed depending on a size of the container and, for example, it can be defined as 0.2 to 50% of a length of from the base of the inflow port to the base of the outflow port.
  • a volume of the space portion at one side is preferably in the range of 0.2 to 50% of an entire volume and a total volume of the space portions at both sides is preferably in the range of 0.5 to 50% of an entire volume.
  • a cross-sectional area such that a linear velocity of the gas is to be 30 m/sec or less, when passing through a side face ( ⁇ -d-h, wherein d represents a diameter of an inflow port or an outflow port; h represents a height of an imaginary column in a space portion) of an imaginary column (10) to be formed by a plane which is vertically dropped from a peripheral line of an inflow port or an outflow port of the fluid to a surface of the fluid permeating plate, and such that a maximum flow rate
  • a pressure loss becomes large, and accordingly, a flow rate per hour to be treated lowers.
  • a flow rate when the fluid passes at a narrowest place is set to 15 m/sec or less.
  • a linear velocity of the fluid which passes through the side face of the imaginary column (10) varies depending on a flow rate of the fluid passing through an entire column. Therefore, at the timeofdesigning, thepassingspeedatthesidefaceoftheimaginary column is arranged to be 30 m/sec or less at a flow rate conceivable in an actual use.
  • a lower limit of the passing speed at the side face of the imaginary column is not particularly defined so long as the fluid containing the compound can flow without anypractical problem. Furthermore, it is preferable that the projected structure (8) for imparting an open space is in contact with the fluid permeating plate in a smaller area because the pressure loss is reduced.
  • the packing materials to be used in the present invention range widely from a silica gel type to an organic polymer type, alumina, zeolite, hydroxyapatite, activated carbon, silicon carbide and the like. Shapes thereof have a wide variety such as a porous spherical particle, a crushed particle, fiber and a rod-like porous continuous body (monolith) .
  • One of characteristics of the fiber or monolith is a small pressurelossatthetimeofliquid-passing.
  • Onecantakeadvantage of the characteristic by using the fiber or monolith in the purification-concentration device according to the present invention since the resistance at the time of liquid-passing attributable to the structure is decreased and therefore liquid-passing is not obstructed.
  • an average particle diameter is allowed to be decreased; however, when the average particle diameter comes to be 5 ⁇ m or less, the resistance at the time of liquid-passing increases regardless of the structure of the purification-concentration device, which is not preferable.
  • the particle thereof is expanded when it comes into contact with the fluid, which accompanies volume change of the packing material.
  • the fluid permeating plate is push-expanded at the time of liquid-passing.
  • the space portions are constitutionally provided at the outer sides of the fluid permeatingplates, the fluidpermeatingplate is tightlyin contact with the inner wall of the container and, accordingly, the passing property of the liquid is not impaired.
  • the purification-concentration device according to the invention in a case of the packing material having volume change of 0.5 to 50%.
  • Forms of the compound concentration devices according to the invention are not particularly limited and representative examples include a column, a cartridge, a disk, a filter, a plate and a capillary.
  • the compounds to be purified and concentrated (separated) according to the invention include one or more compounds selected from the group consisting of compounds present in environmental water, a bottom sediment or atmospheric air such as dioxins, endocrine disturbing chemicals, a biotoxin and an agricultural chemical; compounds present in a biological fluid or a tissue of an animal or a plant such as a medicine, an agricultural chemical, a surfactant, a hormone, a neurotransmitter, a vitamin and a metabolite thereof; and compounds contained in a natural product such as a natural medicine, a natural coloring agent, a natural fragrance and a natural seasoning.
  • compounds present in environmental water, a bottom sediment or atmospheric air such as dioxins, endocrine disturbing chemicals, a biotoxin and an agricultural chemical
  • compounds present in a biological fluid or a tissue of an animal or a plant such as a medicine, an agricultural chemical, a surfactant, a hormone, a neurotransmitter, a vitamin and a metabolite thereof
  • liquids or gases containing compounds to be separated examples are environmental water such as rainwater, streamwater, lakewater, cleanwater, sewage, industrial effluent and sea water; a biological fluid such as urine and blood, or a separated liquid or an extracted liquid thereof; an extracted liquid from a tissue of a plant or an animal; and an environmental atmospheric air such as an incinerator flue gas, emission gases from various types of production facilities, an indoor air, an automobile exhaust gas, an atmospheric air collected above an arterial highway or an absorbed liquid prepared by allowing such air or gas as described above to be passed through a liquid.
  • environmental water such as rainwater, streamwater, lakewater, cleanwater, sewage, industrial effluent and sea water
  • a biological fluid such as urine and blood, or a separated liquid or an extracted liquid thereof
  • an extracted liquid from a tissue of a plant or an animal examples are environmental atmospheric air such as an incinerator flue gas, emission gases from various types of production facilities, an indoor air, an automobile exhaust gas, an atmospheric air collected above an arterial highway or an
  • Themethodforpurifyingandconcentratingthecompoundusing the compound purification-concentration device according to the invention is not particularly limited, so long as a main object thereof is, by allowing a liquid or a gas containing a compound (a material to be measured or a useful material) to pass through, to perform purification by adsorbing a material which obstructs a measurement of the compound or to perform purification and/or concentration after a compound is once adsorbed by the packing material, byelutingthecompoundwithasolvent.
  • Atypicalexample is capturing andconcentrating an environmental pollutantbyusing a cartridge for solid phase extraction.
  • a cartridge prepared by filling a packing material and the fluid permeating plates for holding the packing material in a syringe type container made of polyethylene or the like can be used.
  • a specified device for coupling is required.
  • a volume of a filling portion including fluid permeatingplates is limitedin suchcartridges duetoarestriction on designing.
  • the cartridge according to the invention is extremely useful.
  • a cartridge having an inner diameter of about 12 mm about 300 mg of polystyrene particles having a diameter of 500 to 700 ⁇ m was filled being sandwiched and held by two fluid permeating plates prepared by sintering polyethylene particles.
  • a tapered structure was provided such that a space having a height of about 2 mm at a central portion is formed.
  • the cartridge was connected with a vacuum pump and aeration wasperformedbya suckingmethod, andsubsequently, adifferential pressure between an upstream side and a downstream side of the cartridge was measured while changing the aeration rate.
  • the aeration linear velocity at the side face of the imaginary column was 10.6 m/sec and the differential pressure of the cartridge was about 90 hPa.
  • the cartridge was connected with a vacuum pump and aeration was performed by a sucking method, and subsequently, a differential pressure between an upstream side and a downstream side of the cartridge was measured while changing the aeration rate.
  • a cartridge (filled with about 300 mg of polystyrene particles having a diameter of 500 to 700 ⁇ m) , as schematically shown in FIG.2, having a same diameter as in Example 1 but without having a tapered structure was prepared. Byusing this cartridge, a test was performed in the same way. When aeration was performed at an aeration rate of 3 L/min, a differential pressure of the cartridge was about 108 hPa. A measurement was unable to be performed at a higher flow rate than the above described rate, due to being out of a practical measuring range.
  • a cartridge (filled with about 300 mg of polystyrene particles having a diameter of 500 to 700 ⁇ m) having a same diameter as in Example 1 and having a structure forming a space having a height of about 0.5 mm at a central portion at each of the outer surface sides of the both fluid permeating plates was prepared.
  • a cartridge of the same type as used in Example 1 about 300 mg of polystyrene particles having a diameter of 50 to 90 ⁇ m was filledbeing sandwichedandheldby two fluidpermeatingplates produced by sintering polyethylene particles.
  • the cartridge was connected with a metering pump and then purified water was allowed to pass by a pressure method, and thereafter, a pressure at an upstream side of the cartridge was measured while changing liquid-passing rate.
  • the pressure at the upstream side of the cartridge was about 85 hPa, about 160 hPa and about 330 hPa when a liquid was allowed to pass at a liquid-passing rate of 10 mL/min, 20 mL/min and 40 mL/min, respectively.
  • Example 4 In a cartridge of the same type as used in Comparative Example 1, about 300 mg of polystyrene particles having a diameter of 50 to 90 ⁇ mwas filledbeing sandwichedandheldbytwo fluidpermeating plates produced by sintering polyethylene particles. By using this cartridge, a same test as in Example 2 was performed. As a result, the pressure at the upstream side of the cartridge was about 160 hPa, about 240 hPa and about 420 hPa when a liquid was allowed to pass at a liquid-passing rate of 10 mL/min, 20 mL/min and 40 mL/min, respectively.
  • Example 4 Example 4
  • bendiocarb was eluted by using 10 mL of acetone/ethyl acetate (1:1) and the resultant solution was concentrated into 0.5 mL by gently blowing a nitrogen gas, and then made up to be 3 mL with acetonitrile, and thereafter subjectedtoanalysisbyan HPLC (UV: 254 nm) todetermine a recovery rate.
  • the compound concentration device according to the present invention is used in purification and/or concentration of a compound such as endocrine disturbing chemicals, agricultural chemicals or pharmaceuticals contained in gas or liquid and, in any of these cases, can attain the object quickly in a short period of time.

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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)
  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

La présente invention porte sur un dispositif d’épuration et de concentration de composé, ayant un matériau de garniture pour épurer et concentrer un composé et une plaque de pénétration de fluide pour maintenir le matériau de garniture à chaque surface d’extrémité du matériau de garniture dans un conteneur possédant un orifice d’entrée et un orifice de sortie pour un fluide, caractérisé par une portion d’espace à une surface externe de la plaque de pénétration de fluide à chaque surface d’extrémité, et un procédé d’épuration et de concentration utilisant le dispositif. Dans la présente invention, le dispositif est conçu pour que si le fluide est un gaz et s’écoule à un débit compris entre 6 et 12 L/min, une vitesse linéaire du gaz passant par une face latérale d’une colonne imaginaire formée par un plan tombant verticalement d’une ligne périphérique de l’orifice d’entrée ou de l’orifice de sortie du fluide à la surface de la plaque de pénétration de fluide soit inférieure ou égale à 30 m/sec. Le dispositif d’épuration et de concentration de composé de la présente invention est caractérisé en ce que, tout en maintenant une capacité élevée d’épuration et de séparation d’un composé, la pression générée au moment du passage de gaz ou du passage de liquide est relativement basse et l’obstruction est moindre, même avec un échantillon ayant de nombreux solides en suspension.
PCT/JP2005/016175 2004-08-31 2005-08-30 Dispositif pour épurer et concentrer un composé et procédé pour épurer et concentrer un composé à l’aide du dispositif Ceased WO2006025557A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2004-252420 2004-08-31
JP2004252420 2004-08-31
US60759804P 2004-09-08 2004-09-08
US60/607,598 2004-09-08
JP2004322078 2004-11-05
JP2004-322078 2004-11-05

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WO2006025557A1 true WO2006025557A1 (fr) 2006-03-09

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PCT/JP2005/016175 Ceased WO2006025557A1 (fr) 2004-08-31 2005-08-30 Dispositif pour épurer et concentrer un composé et procédé pour épurer et concentrer un composé à l’aide du dispositif

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9494496B2 (en) 2011-07-08 2016-11-15 Hitachi High-Technologies Corporation Solid-phase extraction apparatus and viscosity measurement apparatus

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5176721A (en) * 1990-10-11 1993-01-05 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Adsorber and process for the separation by adsorption
GB2329597A (en) * 1995-02-15 1999-03-31 Air Liquide Arrangement of a retaining grille of an active material in a vessel, and a vessel so equipped
US6070653A (en) * 1996-03-04 2000-06-06 Aga Aktiebolag Cylindrical vessel for separation
US6517613B1 (en) * 1998-11-10 2003-02-11 Metallgesellschaft Ag Tank for containing granular absorbers for cleaning gases

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5176721A (en) * 1990-10-11 1993-01-05 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Adsorber and process for the separation by adsorption
GB2329597A (en) * 1995-02-15 1999-03-31 Air Liquide Arrangement of a retaining grille of an active material in a vessel, and a vessel so equipped
US6070653A (en) * 1996-03-04 2000-06-06 Aga Aktiebolag Cylindrical vessel for separation
US6517613B1 (en) * 1998-11-10 2003-02-11 Metallgesellschaft Ag Tank for containing granular absorbers for cleaning gases

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9494496B2 (en) 2011-07-08 2016-11-15 Hitachi High-Technologies Corporation Solid-phase extraction apparatus and viscosity measurement apparatus

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