EP1314026A2 - Chromatographie et autres procedes d'adsorption dans lesquels on utilise des adsorbants au carbone modifies - Google Patents

Chromatographie et autres procedes d'adsorption dans lesquels on utilise des adsorbants au carbone modifies

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Publication number
EP1314026A2
EP1314026A2 EP01968422A EP01968422A EP1314026A2 EP 1314026 A2 EP1314026 A2 EP 1314026A2 EP 01968422 A EP01968422 A EP 01968422A EP 01968422 A EP01968422 A EP 01968422A EP 1314026 A2 EP1314026 A2 EP 1314026A2
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EP
European Patent Office
Prior art keywords
organic group
separation device
carbonaceous material
group
attached
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01968422A
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German (de)
English (en)
Inventor
Agathagelos Kyrlidis
Steven R. Reznek
James A. Belmont
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.)
Cabot Corp
Original Assignee
Cabot Corp
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Filing date
Publication date
Application filed by Cabot Corp filed Critical Cabot Corp
Publication of EP1314026A2 publication Critical patent/EP1314026A2/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D57/00—Separation, other than separation of solids, not fully covered by a single other group or subclass, e.g. B03C
    • B01D57/02—Separation, other than separation of solids, not fully covered by a single other group or subclass, e.g. B03C by electrophoresis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3253—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3285—Coating or impregnation layers comprising different type of functional groups or interactions, e.g. different ligands in various parts of the sorbent, mixed mode, dual zone, bimodal, multimodal, ionic or hydrophobic, cationic or anionic, hydrophilic or hydrophobic
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/447—Systems using electrophoresis
    • G01N27/44704—Details; Accessories
    • G01N27/44747—Composition of gel or of carrier mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography

Definitions

  • This invention relates to separation devices and processes as well as the use of modified carbonaceous materials as adsorbents and also relates to methods of using these adsorbents, including a method to increase the adsorption capacity and/or alter the adsorption affinity of carbonaceous materials capable of adsorbing an adsorbate.
  • Adsorption is an important operation in many industrial processes.
  • the effectiveness of an adsorbent depends, primarily, on its surface area, pore structure, and surface chemistry.
  • carbonaceous adsorbents are often used to selectively remove organic compounds from liquid, gaseous, or vapor media.
  • Silica and alumina based adsorbents are employed to selectively adsorb polar adsorbates such as water, ammonia, and the like from similar media.
  • the efficacy of an adsorbent for a particular application is usually determined by the adsorption capacity and selectivity of the adsorbent for the adsorbate in question.
  • the adsorption capacity may be measured per unit mass or per unit volume ofthe adsorbent.
  • Carbonaceous materials, such as activated carbon, carbon black, and the like, represent an important class of adsorbents which are used in many fields such as separation, purification, and waste treatment, among others.
  • any method for improving the adsorption properties of carbonaceous adsorbents for a particular adsorbate can have a large impact on the efficacy and economy of the processes utilizing them. Therefore, attempts have been made in the past to modify the surface chemistry of carbonaceous adsorbents.
  • the methods employed for their modification can be broadly classified into physical and chemical means.
  • surface modification by physical means a species is deposited on the surface ofthe carbonaceous adsorbent to form a layer which then changes its adsorption properties.
  • modification techniques have limited utility because the deposited layer is easily removed.
  • the modifying species is attached to the carbon surface by a chemical bonding mechanism.
  • the characteristics of the adsorption isotherm representing the relationship between the extent of adsorption and adsorbate concentration or adsorbate partial pressure at a fixed temperature, is also of importance.
  • the characteristics of the preferred adsorption isotherm will depend on the separation process being employed. For example, in cases where adsorbent regeneration is effected by a pressure swing, the preferred adsorbent is one with a moderate affinity for the adsorbate. When the adsorbate is strongly adsorbed, that is, when it has a strong affinity for the adsorbent, regeneration becomes difficult and energy intensive.
  • the adsorbent when the adsorbent exhibits a weak affinity for the adsorbate, it has a small adsorption capacity at low adsorbent partial pressures and, hence, the adsorption mass transfer zone becomes very long.
  • the availability of a method for altering the affinity of an adsorbent for an adsorbate is advantageous.
  • any method for increasing the adsorption capacity and/or modifying the adsorption affinity of the adsorbent enhances its usefulness in adsorption applications.
  • chemical modification can be used to alter the adsorptive properties of carbonaceous adsorbents.
  • the range of chemical species which can be attached, however, is limited.
  • Bansal, Donnet and Stoeckli have reviewed different techniques of carbon surface modification. Physical impregnation methods are described, as are methods that rely on chemical reactions with various species to modify the surface of the carbon. Some of the chemical surface modification techniques described by Bansal et al. are oxidation, halogenation, sulfonation, and ammoniation. Several of these techniques require treatment of the carbon at elevated temperatures. Another technique involving oxidation of the carbon with HN0 3 in the presence of a catalyst, has been described by Sircar and Golden (U.S. Patent No.4,702,749). However, these techniques have certain disadvantages apparent to those familiar with the field.
  • the present invention relates to an adsorbent composition containing a modified carbonaceous material capable of adsorbing an adsorbate.
  • the present invention also relates to a separation device having a mobile phase and a stationary phase, wherein said stationary phase is a carbonaceous material having attached at least one organic group.
  • the carbonaceous material having attached at least one organic group is capable of adsorbing one or more chemical species present in a mixture.
  • the present invention further relates to a chromatography column containing a column having a stationary phase and a mobile phase.
  • the stationary phase is at least a carbonaceous material having attached at least one organic group wherein the carbonaceous material having at least one organic group is capable of adsorbing at least one chemical species present in a mixture.
  • the present invention further relates to a method for conducting chromatography on a substance and involves passing the substance through a column having a stationary phase and a mobile phase, wherein the stationary phase is at least a carbonaceous material having attached at least one organic group.
  • the chromatography can be, for instance, a size exclusion chromatography, an affinity-type chromatography, an adsorption-desorption chromatography, or variations thereof or combinations thereof.
  • the chromatography can be a reverse phase chromatography, ion exchange chromatography, supercritical fluid chromatography, hydrophobic interaction chromatography, or chiral chromatography.
  • the present invention in addition, relates to bioseparations using the chromatography methods described above.
  • the present invention also relates to separations using electrophoresis wherein the stationary phase is a carbonaceous material having attached at least one organic group.
  • the present invention further relates to a separation device containing a membrane wherein said membrane contains a carbonaceous material having attached at least one organic group.
  • the separation device can also be a magnetic separation device or a reverse osmosis device wherein the stationary phase or the membrane contains a carbonaceous material having attached at least one organic group.
  • Another embodiment of the present invention relates to a method to increase the adsorption capacity of a carbonaceous material capable of adsorbing an adsorbate or altering the adsorption isotherm of the adsorbate on the adsorbent, for instance, to allow an easier regeneration of the adsorbent.
  • this method at least one organic group capable of increasing the adsorption capacity of a carbonaceous material is attached to the carbonaceous material.
  • the present invention in addition, relates to a method of adsorbing an adsorbate and includes the step of contacting the adsorbate with a carbonaceous material which has been modified by attaching an organic group.
  • the modified carbonaceous material is capable of adsorbing the adsorbate and at least one organic group is attached to the carbonaceous material.
  • Figure 1 is a graph plotting the amount of water adsorption on modified and unmodified carbon black.
  • Figure 2 is a graph plotting the amount of water adsorption on modified and unmodified activated carbon.
  • Figure 3 is a graph plotting the amount of water adsorption on modified and unmodified carbon black per unit surface area.
  • Figure 4 is a graph plotting the amount of water adsorption on modified and unmodified activated carbon per unit surface area.
  • Figure 5 is a graph plotting the amount of C0 adsorption on modified and unmodified carbon black at 273 K.
  • Figure 6 is a graph plotting the concentration of supernatant vs. the concentration of loaded Bovine Serum Albumin (BSA) solution in the presence of various carbonaceous materials.
  • Figures 7-1 1 are various graphs plotting the separation of various analytes resulting from using various phases ofthe present invention.
  • the present invention relates to separation devices which typically have a stationary phase.
  • the stationary phase for purposes ofthe present invention, is a carbonaceous material having attached at least one organic group. This material is also known, once the organic group is attached, as a modified carbonaceous material for purposes ofthe present invention.
  • the organic group is preferably attached (e.g., chemically) to the surfaces of the carbonaceous material, preferably by covalent bonds.
  • One preferred separation device is a chromatography column which, for purposes of the present invention, contains a column having a mobile phase and a stationary phase.
  • the stationary phase is at least the modified carbonaceous material ofthe present invention.
  • the mobile phase can be any conventional mobile phase used in the separation of chemical compounds or species from a mixture, such as solvents and the like.
  • the present invention further relates to a method for conducting chromatography on a substance or mixture which involves passing the substance through a column packed with at least the modified carbonaceous material as the stationary phase and the mobile phase.
  • the type of chromatography that can be accomplished by 'the present invention includes, but is not limited to, size exclusion chromatography and affinity chromatography (wherein the affinity between the modified carbonaceous material and the different chemical species in the mixture is different such that separation occurs at different rates).
  • Another type of chromatography that can be accomplished by the present invention is adsorption-desorption chromatography, reverse phase chromatography, ion exchange chromatography, hydrophobic interaction chromatography, chiral chromatography, capillary liquid chromatography, supercritical fluid chromatography, or electrochromatography.
  • Chromatographic separation of proteins and other biomolecules can also be accomplished by the present invention.
  • An example of such a bioseparation would involve the use of a stationary phase wherein polyols or polyethylene glycol compounds are attached on the carbonaceous material.
  • Another example of a bioseparation would involve the use of a stationary phase wherein benzoic acid or benzenesulfonic groups are attached to the surface ofthe carbonaceous material.
  • a chromatographic system typically contains a mobile phase, a stationary phase, a pumping system, and a detector.
  • the stationary phase contains insoluble particles which are preferably spherical and preferably range in size from about 1 micron to about 500 microns, and most preferably 2 to 5 microns, for analytical chromatography and 10 to 40 microns for preparative chromatographic applications. These particles have a surface area ranging from about 1 to about 500 m /g. preferably 50 to 200 m /g, and a mean pore diameter ranging from about 20 to about 20,000 Angstrom, preferably 60 to 1000 Angstrom. The choice of these particles depends on the physical, chemical, and/or biological interactions that need to be exploited by the separation.
  • Another form of separation is electrophoresis which uses an applied electric field to produce directed movement of charged molecules.
  • electrophoresis can be accomplished by using a stationary phase which contains the modified carbonaceous material ofthe present invention.
  • magnetic separations such as magnetic bioseparations, can be accomplished using the modified magnetic carbonaceous materials of the present invention as the stationary phase.
  • membrane separations such as reverse osmosis
  • membrane separations can be accomplished by forming the membrane such that it contains modified carbonaceous materials.
  • the membrane can be formed by dispersing the modified carbonaceous material in a polymer and casting the polymer mixture to form a membrane.
  • Another way to make the membrane is to form a conventional membrane and then surface modify the membrane to attach organic groups onto the membrane.
  • Membranes can be used in a variety of separation techniques, including protein separations and/or metal removal.
  • any separation technique which involves the use of a stationary phase can be improved by the present invention.
  • the stationary phase can be or can contain the modified carbonaceous material of the present invention.
  • an adsorbent composition of the present invention contains a modified carbonaceous material capable of adsorbing an adsorbate wherein at least one organic group is attached to the carbonaceous material.
  • the carbonaceous material capable of adsorbing an adsorbate includes, but is not limited to, activated carbon, carbon black, graphite, or other carbonaceous material obtained by the pyrolysis of cellulosic, fuel oil, polymeric, or other precursors.
  • Additional examples include but are not limited to, carbon fibers, carbon cloth, vitreous carbon, carbon aerogels, pyrolized ion exchange resins, pyrolized polymer resins, mesoporous carbon microbeads, pelleted carbon powder, nanotubes, buckyballs, silicon-treated carbon black, silica-coated carbon black, metal-treated carbon black, densified carbon black, carbon clad silica, alumina, and ceria particles, and combinations thereof or activated versions thereof.
  • the carbonaceous material can also be a waste product or by-product of carbonaceous material obtained by pyrolysis, including carbonized polymeric particles (e.g., polydivinylbenzene based chromatographic particles, or sulfonated polydivinylbenzene/polystyrene particles).
  • the carbonaceous material is • activated carbon or carbon black capable of adsorbing an adsorbate.
  • Commercial examples of carbon black include, but are not limited to, Black Pearls® 2000 carbon black, Black Pearls® 430 carbon black, Black Pearls® 900 carbon black, and Black Pearls® 120 carbon black, all available from Cabot Corporation.
  • activated carbon examples include Darco S51, available from Norit; Sorbonorit 3, available from Norit; Ambersorb adsorbent (available from Rohm and Haas); Hypercarb carbon particle (available from ThermoHyperSil); TosoHaas carbon materials; and BPL activated carbon from Calgon.
  • the carbonaceous material modified by the procedures described herein may be a microporous or mesoporous activated carbon in granular or pellet form; a carbon black of different structures in fluffy or pelleted form; or any other carbonaceous material whose applicability to this invention is apparent to those skilled in the art, such as carbon fibers or carbon cloth.
  • carbonaceous material used eventually depends on a variety of different factors, including the application for which it is intended. Each of these types of carbonaceous material has the ability to adsorb at least one adsorbate. A variety of BET surface areas, micropore volumes, and total pore volumes are available depending on the desired end use ofthe carbonaceous material.
  • Carbonaceous materials include, but are not limited to, material obtained by the compaction of small carbon particles and other finely divided forms of carbon as long as the carbon has the ability to adsorb at least one adsorbate and is capable of being chemically modified in accordance with the present invention.
  • the carbonaceous material can be an aggregate comprising a carbon phase and a silicon-containing species phase. A description of this aggregate as well as means of making this aggregate is described in PCT Publication No. WO 96/37547 and WO 98/47971 as well as U.S. Patent Nos. 5,830,930; 5,869,550; 5,877,238; 5,919,841 ; 5,948,835; and 5,977,213. All of these patents and publications are hereby incorporated in their entireties herein by reference.
  • the carbonaceous material for purposes of the present invention can also be an aggregate comprising a carbon phase and metal-containing species phase where the metal- containing species phase can be a variety of different metals such as magnesium, calcium, titanium, vanadium, cobalt, nickel, zirconium, tin, antimony, chromium, neodymium, lead, tellurium, barium, cesium, iron, molybdenum, aluminum, and zinc, and mixtures thereof.
  • the aggregate comprising the carbon phase and a metal-containing species phase is described in U.S. Patent No. 6,017,980, also hereby incorporated in its entirety herein by reference.
  • the carbonaceous material includes a silica-coated carbon black, such as that described in U.S. Patent No. 5,916,934 and PCT Publication No. WO 96/37547, published November 28, 1996, also hereby incorporated in their entirety herein by reference.
  • the carbonaceous material described above is then modified by the attachment of an organic group to the carbonaceous material.
  • Preferred processes for attaching an organic group to a carbonaceous material and examples or organic groups are described in detail in U.S. Patent Nos. 5,554,739; 5,559,169; 5,571,311; 5,575,845; 5,630,868; 5,672,198; 5,698,016; 5,837,045; 5,922, 118; 5,968,243; 6,042,643; 5,900,029; 5,955,232; 5,895,522; 5,885,335; 5,851,280; 5,803,959; 5,713,988; and 5,707,432; and International Patent Publication Nos.
  • These processes can be preferably used in preparing the modified carbon adsorbents ofthe present invention and permit the attachment of an organic group to the carbonaceous material via a chemical reaction.
  • the organic group attached to the carbonaceous material is one preferably capable of increasing the adsorption capacity and/or selectivity of -l ithe carbonaceous material and/or enhancing the resolution of solute peaks in chromatographic separations.
  • a particular functional group or multiple functional groups can be chosen to be attached onto the carbonaceous material in order to accomplish the selectivity needed to conduct the separation process.
  • heparin is used in the separation of lipoproteins, accordingly, heparin can be attached onto carbonaceous material in order to accomplish the desired separation.
  • a sulfonic acid for instance, can be attached on a carbonaceous material and when anionic exchanges are needed, a quaternary amine can be attached onto the carbonaceous material.
  • the present invention provides a carbonaceous material which is resistant to corrosion, swelling, and/or extreme temperatures and pressures, but also provides the desired selectivity.
  • the present invention gives the separation field the best of both worlds, namely, selectivity combined with a resilient stationary phase without any losses in the efficiency of separation.
  • a preferred process for attaching an organic group to the carbonaceous materials involves the reaction of at least one diazonium salt with a carbonaceous material in the absence of an externally applied current sufficient to reduce the diazonium salt. That is, the reaction between the diazonium salt and the carbonaceous material proceeds without an external source of electrons sufficient to reduce the diazonium salt. Mixtures of different diazonium salts may be used. This process can be carried out under a variety of reaction conditions and in any type of reaction medium, including both protic and aprotic solvent systems or slurries.
  • At least one diazonium salt reacts with a carbonaceous material in a protic reaction medium. Mixtures of different diazonium salts may be used in this process. This process can also be carried out under a variety of reaction conditions. Preferably, in both processes, the diazonium salt is formed in situ. If desired, in either, process, the modified carbonaceous material can be isolated and dried by means known in the art. Furthermore, the modified carbonaceous material can be treated to remove impurities by known techniques. The various preferred embodiments of these processes are discussed below.
  • the processes can be carried out under a wide variety of conditions and in general are not limited by any particular condition.
  • the reaction conditions must be such that the particular diazonium salt is sufficiently stable to allow it to react with the carbonaceous material.
  • the processes can be carried out under reaction conditions where the diazonium salt is short lived.
  • the reaction between the diazonium salt and the carbonaceous material occurs, for example, over a wide range of pH and temperature.
  • the processes can be carried out at acidic, neutral, and basic pH.
  • the pH ranges from about 1 to 9.
  • the reaction temperature may preferably range from 0 ° C to 100 ° C.
  • Diazonium salts may be formed for example by the reaction of primary amines with aqueous solutions of nitrous acid.
  • a general discussion of diazonium salts and methods for their preparation is found in Morrison and Boyd, Organic Chemistry, 5th Ed., pp. 973-983, (Allyn and Bacon, Inc. 1987) and March, Advanced Organic Chemistry: Reactions, Mechanisms, and Structures, 4th Ed., (Wiley, 1992).
  • a diazonium salt is an organic compound having one or more diazonium groups.
  • the diazonium salt may be prepared prior to reaction with the carbonaceous material or, more preferably, generated in situ using techniques known in the art. In situ generation also allows the use of unstable diazonium salts such as alkyl diazonium salts and avoids unnecessary handling or manipulation of the diazonium salt. In particularly preferred processes, both the nitrous acid and the diazonium salt are generated in situ.
  • a diazonium salt may be generated by reacting a primary amine, a nitrite and an acid.
  • the nitrite may be any metal nitrite, preferably lithium nitrite, sodium nitrite, potassium nitrite, or zinc nitrite, or any organic nitrite such as for example isoamylnitrite or ethylnitrite.
  • the acid may be any acid, inorganic or organic, which is effective in the generation ofthe diazonium salt. Preferred acids include nitric acid, HNO 3 , hydrochloric acid, HCl, and sulfuric acid, H 2 S0 .
  • the diazonium salt may also be generated by reacting the primary amine with an aqueous solution of nitrogen dioxide. The aqueous solution of nitrogen dioxide, NO H 2 0, provides the nitrous acid needed to generate the diazonium salt.
  • Generating the diazonium salt in the presence of excess HCl may be less preferred than other alternatives because HCl is corrosive to stainless steel.
  • Generation of the diazonium salt with N0 2 /H 2 0 has the additional advantage of being less corrosive to stainless steel or other metals commonly used for reaction vessels. Generation using
  • H 2 SO /NaN0 2 or HN0 3 /NaN0 2 are also relatively non-corrosive.
  • generating a diazonium salt from a primary amine, a nitrite, and an acid requires two equivalents of acid based on the amount of amine used.
  • the diazonium salt can be generated using one equivalent of the acid.
  • adding a separate acid may not be necessary.
  • the acid group or groups of the primary amine can supply one or both of the needed equivalents of acid.
  • the primary amine contains a strong acid group, preferably either no additional acid or up to one equivalent of additional acid is added to a process of the invention to generate the diazonium salt in situ. A slight excess of additional acid may be used.
  • One example of such a primary amine is para-aminobenzenesulfonic acid (sulfanilic acid).
  • diazonium salts are thermally unstable. They are typically prepared in solution at low temperatures, such as 0-5 ° C, and used without isolation ofthe salt. Heating solutions of some diazonium salts may liberate nitrogen and form either the corresponding alcohols in acidic media or the organic free radicals in basic media.
  • the diazonium salt need only be sufficiently stable to allow reaction with the carbonaceous material.
  • the processes can be carried out with some diazonium salts otherwise considered to be unstable and subject to decomposition.
  • Some decomposition processes may compete with the reaction between the carbonaceous material and the diazonium salt and may reduce the total number of organic groups attached to the carbonaceous material.
  • the reaction may be carried out at elevated temperatures where many diazonium salts may be susceptible to decomposition. Elevated temperatures may also advantageously increase the solubility ofthe diazonium salt in the reaction medium and improve its handling during the process. However, elevated temperatures may result in some loss ofthe diazonium salt due to other decomposition processes.
  • Reagents can be added to form the diazonium salt in situ, to a suspension of carbonaceous material in the reaction medium, for example, water.
  • a carbonaceous material suspension to be used may already contain one or more reagents to generate the diazonium salt and the process accomplished by adding the remaining reagents.
  • Reactions to form a diazonium salt are compatible with a large variety of functional groups commonly found on organic compounds. Thus, only the availability of a diazonium salt for reaction with a carbonaceous material limits the processes ofthe invention.
  • the processes can be carried out in any reaction medium which allows the reaction between the diazonium salt and the carbonaceous material to proceed.
  • the reaction medium is a solvent-based system.
  • the solvent may be a protic solvent, an aprotic solvent, or a mixture of solvents.
  • Protic solvents are solvents, like water or methanol, containing a hydrogen attached to an oxygen or nitrogen and thus are sufficiently acidic to form hydrogen bonds.
  • Aprotic solvents are solvents which do not contain an acidic hydrogen as defined above.
  • Aprotic solvents include, for example, solvents such as hexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile.
  • the processes are preferably carried out in a protic reaction medium, that is, in a protic solvent alone or a mixture of solvents which contains at least one protic solvent.
  • Preferred protic media include, but are not limited to water, aqueous media containing water and other solvents, alcohols, and any media containing an alcohol, or mixtures of such media.
  • the reaction between a diazonium salt and a carbonaceous material can take place with any type of carbonaceous material, for example, in finely divided state or pelleted form. In one embodiment designed to reduce production costs, the reaction occurs during a process for forming carbonaceous material pellets.
  • a carbonaceous material product ofthe invention can be prepared in a dry drum by spraying a solution or slurry of a diazonium salt onto a carbonaceous material.
  • the carbonaceous material product can be prepared by pelletizing a carbonaceous material in the presence of a solvent system, such as water, containing the diazonium salt or the reagents to generate the diazonium salt, in situ.
  • a solvent system such as water
  • the processes produce inorganic by-products, such as salts. In some end uses, such as those discussed below, these by-products may be undesirable.
  • the diazonium salt can be purified before use by removing the unwanted inorganic by-product using means known in the art.
  • the diazonium salt can be generated with the use of an organic nitrite as the diazotization agent yielding the corresponding alcohol rather than an inorganic salt.
  • the diazonium salt is generated from an amine having an acid group and aqueous N0 2 , no inorganic salts are formed. Other ways may be known to those of skill in the art.
  • the process may also produce organic by-products. They can be removed, for example, by extraction with organic solvents. Other ways of obtaining products without unwarranted organic by-products may be known to those of skill in the art, and include washing or removal of ions by reverse osmosis.
  • the reaction between a diazonium salt and a carbonaceous material forms a carbonaceous material product having an organic group attached to the carbonaceous material.
  • the diazonium salt may contain the organic group to be attached to the carbonaceous material.
  • the organic group may be an aliphatic group, a cyclic organic group, or an organic compound having an aliphatic portion and a cyclic portion.
  • the diazonium salt employed can be derived from a primary amine having one of these groups and being capable of forming, even transiently, a diazonium salt.
  • the organic group may be substituted or unsubstituted, branched or unbranched.
  • Aliphatic groups include, for example, groups derived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids, and carbohydrates.
  • Cyclic organic groups include, but are not limited to, alicyclic hydrocarbon groups (for example, cycloalkyls, cycloalkenyls), heterocyclic hydrocarbon groups (for example, pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like), aryl groups (for example, phenyl, naphthyl, anthracenyl, and the like), and heteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, furyl, indolyl, and the like).
  • alicyclic hydrocarbon groups for example, cycloalkyls, cycloalkenyls
  • heterocyclic hydrocarbon groups for example, pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like
  • aryl groups for example, phenyl, naphthyl, anthrac
  • organic group When the organic group is substituted, it may contain any functional group compatible with the formation of a diazonium salt.
  • R and R' which can be the same or different, are independently hydrogen, branched or unbranched Ci- C 20 substituted or unsubstituted, saturated or unsaturated hydrocarbon, e.g., alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylaryl, or substituted or unsubstituted arylalkyl.
  • the integer k ranges from 1-8 and preferably from 2-4.
  • the anion X " is a halide or an anion derived from a mineral or organic acid.
  • Q is (CH 2 ) W , (CH 2 ) ⁇ O(CH 2 ) 2 , (CH 2 ) X NR(CH 2 ) Z , or (CH ) x S(CH 2 )z, where w is an integer from 2 to 6 and x and z are integers from 1 to 6.
  • R and R' are NH 2 -C 6 H4-, CH 2 CH 2 -C 6 H 4 -NH 2 , CH 2 -C 6 H 4 -NH 2 , and C 6 H 5 .
  • Another example of an organic group is an aromatic group of the formula A y Ar-, which corresponds to a primary amine of the formula A y ArNH 2 .
  • Ar is an aromatic radical such as an aryl or heteroaryl group.
  • Ar can be selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl, benzothiadiazolyl, and benzothiazolyl;
  • A is a substituent on the aromatic radical independently selected from a preferred functional group described above or A is a linear, branched or cyclic hydrocarbon radical (preferably containing 1 to 20 carbon atoms), unsubstituted or substituted with one or more of those functional groups; and y is an integer from 1 to the total number of -CH radicals in the aromatic radical.
  • y is an integer from 1 to 5 when Ar is phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 when Ar is anthracenyl, phenanthrenyl, or biphenyl, or 1 to 4 when Ar is pyridinyl.
  • Another set of organic groups which may be attached to the carbonaceous material are organic groups substituted with an ionic or an ionizable group as a functional group.
  • An ionizable group is one which is capable of forming an ionic group in the medium of use.
  • the ionic group may be an anionic group or a cationic group and the ionizable group may form an anion or a cation.
  • Ionizable functional groups forming anions include, for example, acidic groups or salts of acidic groups.
  • the organic groups therefore, include groups derived from organic acids.
  • an ionizable group forming an anion such an organic group has a) an aromatic group or a C1-C12 alkyl group and b) at least one acidic group having a pKa of less than 11 , or at least one salt of an acidic group having a pKa of less than 1 1, or a mixture of at least one acidic group having a pKa of less than 11 and at least one salt of an acidic group having a pKa of less than 11.
  • the pKa of the acidic group refers to the pKa of the organic group as a whole, not just the acidic substituent. More preferably, the pKa is less than 10 and most preferably less than 9.
  • the aromatic group or the Ci- C ⁇ alkyl group ofthe organic group is directly attached to the carbonaceous material.
  • the aromatic group may be further substituted or unsubstituted, for example, with alkyl groups.
  • the organic group can be a phenyl or a naphthyl group and the acidic group is a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, or a carboxylic acid group.
  • the organic group may also contain one or more asymmetric centers.
  • the organic group can be a substituted or unsubstituted sulfophenyl group or a salt thereof; a substituted or unsubstituted (polysulfo)phenyl group or a salt thereof; a substituted or unsubstituted sulfonaphthyl group or a salt thereof; or a substituted or unsubstituted (polysulfo)naphthyl group or a salt thereof.
  • An example of a substituted sulfophenyl group is hydroxysulfophenyl group or a salt thereof.
  • Specific organic groups having an ionizable functional group forming an anion are p- sulfophenyl (p-sulfanilic acid), 4-hydroxy-3-sulfophenyl (2-hydroxy-5-amino- benzenesulfonic acid), and 2-sulfoethyl (2-aminoethanesulfonic acid).
  • Amines represent examples of ionizable functional groups that form cationic groups.
  • amines may be protonated to form ammonium groups in acidic media.
  • an organic group having an amine substituent has a pKb of less than 5.
  • Quaternary ammonium groups ( ⁇ NR 3 ) and quaternary phosphonium groups (-PR 3 ) also represent examples of cationic groups.
  • the organic group can contain an aromatic group such as a phenyl or a naphthyl group and a quaternary ammonium or a quaternary phosphonium group.
  • the aromatic group is preferably directly attached to the carbonaceous material. Quaternized cyclic amines, and even quaternized aromatic amines, can also be used as the organic group.
  • N-substituted pyridinium compounds such as N-methyl- pyridyl
  • organic groups include, but are not limited to, (C 5 H 4 N)C 2 H 5 + X " , C 6 H 4 (NC 5 H 5 ) + X " , C 6 H 4 COCH 2 N(CH 3 ) 3 + X " , C6H 4 COCH 2 (NC 5 H5) + X " , (C 5 H 4 N)CH 3 + X " , and
  • Aromatic sulfides encompass another group of organic groups. These aromatic sulfides can be represented by the formulas Ar(CH 2 ) q Sk(CH 2 ) r Ar' or A-(CH 2 )qS ⁇ (CH 2 ) r Ar" wherein Ar and Ar' are independently substituted or unsubstituted arylene or heteroarylene groups, Ar" is an aryl or heteroaryl group, k is 1 to 8 and q and r are 0-4. Substituted aryl groups would include substituted alkylaryl groups. Examples of arylene groups include phenylene groups, particularly p-phenylene groups, or benzothiazolylene groups.
  • Aryl groups include phenyl, naphthyl and benzothiazolyl.
  • the number of sulfurs present, defined by k preferably ranges from 2 to 4.
  • Examples of carbonaceous material products are those having an attached aromatic sulfide organic group ofthe formula -(C 6 H 4 )-S -(C6H4)-, where k is an integer from 1 to 8, and more preferably where k ranges from 2 to 4.
  • Other examples of aromatic sulfide groups are bis-para-(C6H4)-S 2 -(C6H )- and para-(C6H 4 )-S -(C6Hs).
  • the diazonium salts of these aromatic sulfide groups may be conveniently prepared from their corresponding primary amines, H 2 N-Ar-Sk-Ar'-NH 2 or H 2 N-Ar-S k -Ar".
  • Groups include dithiodi-4, 1 -phenylene, tetrathiodi-4J -phenylene, phenyldithiophenylene, dithiodi-4J-(3- chlorophenylene), -(4-C 6 H 4 )-S-S-(2-C7H4NS), -(4-C6H4)-S-S-(4-C 6 H 4 )-OH, -6-(2-C 7 H 3 NS)- SH, -(4-C6H4)-CH 2 CH 2 -S-S-CH 2 CH 2 -(4-C 6 H4)-, -(4-C6H 4 )-CH 2 CH2-S-S-S-CH 2 CH 2 -(
  • organic groups which may be attached to the carbonaceous material are organic groups having an aminophenyl, such as (C 6 H 4 )-NH , (C6H 4 )-CH 2 -(C6H 4 )-NH , (C 6 H 4 )-S0 2 -(C6H 4 )-NH 2 .
  • the organic group is a Ci-Cioo alkyl group (more preferably a C1-C12 alkyl group), an aromatic group, or other organic group, monomeric group, or polymeric group, each optionally having a functional group or ionic or ionizable group. More preferably, these groups are directly attached to the carbonaceous material.
  • the polymeric group can be any polymeric group capable of being attached to a carbon product.
  • the polymeric group can be a polyolefin group, a polystyrenic group, a polyacrylate group, a polyamide group, a polyester group, or mixtures thereof.
  • Monomeric groups are monomeric versions ofthe polymeric groups.
  • the organic group can also be an olefin group, a styrenic group, an acrylate group, an amide group, an ester, or mixtures thereof.
  • the organic group can also be an aromatic group or an alkyl group, either group with an olefin group, a styrenic group, an acrylate group, an amide group, an ester group, or mixtures thereof, wherein preferably the aromatic group, or the alkyl group, like a C ⁇ -C ⁇ 2 group, is directly attached to the carbon product.
  • the polymeric group can include an aromatic group or an alkyl group, like a C ⁇ -C ⁇ 2 group, either group with a polyolefin group, a polystyrenic group, a polyacrylate group, a polyamide group, an polyester group, or mixtures thereof.
  • the organic group can also comprise an aralkyl group or alkylaryl group, which is preferably directly attached to the carbon product.
  • organic groups include a Ci-Cioo alkyl group, and more preferably a C 2 o-C 6 o alkyl group.
  • Preferred mixtures of organic groups include the following:
  • the various organic, monomeric, and polymeric groups described above and below which are part of the modified carbon product can be unsubstituted or substituted and can be branched or linear. Any one or more of these organic groups, after attachment to the carbonaceous material which permits adsorption, and preferably an increase in the adsorption capacity of the carbonaceous material may be used in the present invention.
  • the organic group attached to the carbonaceous material is an acid or base or a salt of an acid or base, and specific examples include phenyl or naphthyl groups having substituents like sulfonic acid and carboxylic acid. Quaternary ammonium can also be used.
  • Most preferred organic groups attached to the carbonaceous material are (C6H 4 )-S0 3 ⁇ Na + , (C ⁇ H 4 )-S0 " K , (C6H 4 )-S0 3 " Li , and the like.
  • an acid-type organic group attachment will be useful in adsorbing basic adsorbates while a base-type organic group attachment will be useful in adsorbing acidic adsorbates.
  • Other preferred organic groups which can be used in the present invention include amino acids and derivatized amino acids (e.g., phenyl alanine and its derivatives), cyclodextrins, immobilized proteins and polyproteins, and the like.
  • organic groups include, but are not limited to, C ⁇ Fs- groups and/or trifluoromethyl-phenyl groups, and bis- trifluorophenyl groups, other aromatic groups with fluorine groups, and the like. These organic groups are particularly preferred with respect to the embodiments of the present invention relating to chromatography and other separation techniques.
  • Other preferred organic groups which are attached onto the carbonaceous material include -Ar-(C n H 2n + ⁇ )x group functionalities, wherein n is an integer of from about 1 to about 30 and x is an integer of from about 1 to about 3. These groups are particularly preferred for purposes of reverse phase chromatography.
  • Another example of an organic group is benzene with a sulfonic group, benzoic groups, isophtalic groups which are particularly useful for cationic exchanges and quaternary amine groups which are particularly preferred for anionic exchanges.
  • Organic groups such as cyclodextrins which are directly attached onto the carbonaceous material or attached through an alkyl group such as C n H 2n + ⁇ chain wherein n is an integer of from about 3 to about 20 and also preferred.
  • alkyl group such as C n H 2n + ⁇ chain wherein n is an integer of from about 3 to about 20 and also preferred.
  • Other groups that can be attached are optically pure amino acids and derivatized amino acids, immobilized proteins, and the like. These types of organic groups are particularly preferred with respect to chiral chromatography.
  • PEG groups polyethyleneglycol (PEG groups) and methoxy-terminated PEG groups as well as derivatized PEG and MPEG groups can be attached onto the carbonaceous material.
  • PEG groups polyethyleneglycol (PEG groups) and methoxy-terminated PEG groups as well as derivatized PEG and MPEG groups can be attached onto the carbonaceous material.
  • organic groups are particularly preferred with respect to affinity and/or hydrophobic interactions chromatography for the separation, for instance, of proteins and polyproteins.
  • organic groups that can be attached, either alone or as an additional group, include -Ar-C(CH3)3, -Ar-(CnH2n)CN)m, wherein Ar is an aromatic group, n is 0 to 20, and m is 1 to 3; - Ar-((CnH2n)C(0)N(H)-CxH2x+l)m, wherein Ar is an aromatic group, n is 0 to 20, x is 0 to 20 and m is 1 to 3; - Ar-((CnH2n)N(H)C(0)- CxH2x+l)m, wherein Ar is an aromatic group, n is 0 to 20, x is 0 to 20 and m is 1 to 3; - Ar-((CnH2n)0-C(0)-N(H)-CxH2x+l)m, wherein Ar is an aromatic group, n is 0 to 20, x is 0 to 20 and m is 1 to 3; - Ar-((CnH2
  • the present invention has the ability to attach organic groups such that the organic groups block out microporosity of the carbonaceous material and thus permits the use of microporous materials for separation techniques, such as chromatography. Accordingly, the present invention permits the use of microporous materials that would otherwise not be chromatographically useful for separations.
  • more than one type of group can be attached onto the carbonaceous material. This is especially useful to fill in any gaps on the surface of the carbonaceous material not having an attached organic group. The filling in of such gaps promotes better selectivity and/or blocks any microporosity that may still exist in the carbonaceous material.
  • the optional second organic group is attached after the first primary organic group is attached and the modified carbonaceous material is preferably purified is described above by removing any by-products that are produced from attaching an organic group onto the carbonaceous material. Afterwards, the second organic group can then be attached using the same diazonium salt or other attachment methods.
  • the type of secondary organic groups which are subsequently attached include, but are not limited to, organic groups which are shorter in chain length or have less steric hindrance than the first organic group attached.
  • preferred secondary organic groups include, but are not limited to, phenyl groups, alkyl phenyl groups having short alkyl chains (e.g., Ci- C15), and the like.
  • Particularly preferred groups include, phenyl, methyl-phenyl, 3,5- dimethyl-phenyl, 4-isopropyl-phenyl, and 4-tert-butyl-phenyl.
  • the modified carbonaceous materials of the present invention especially when the attached organic groups are alkyl phenyl groups, like 4-alkyl-phenyl, where the length ofthe alkyl chain is between 1 and 30, (preferably between 8 or 18), are especially useful for reverse phase chromatography applications having surface properties directly analogous to octadecyl-modified silica.
  • the modified carbonaceous materials described above can have secondary attached groups such as phenyl, methyl-phenyl, dimethyl-phenyl, isopropyl-phenyl, tert-butyl-phenyl, and the like.
  • the carbonaceous materials of the present invention will have one or more of the following properties compared to the conventional octadecyl silica:
  • Enhanced pH stability (octadecyl silica is only used in a narrow pH and rarely above pH 8).
  • the enhanced carbonaceous materials ofthe present invention will be stable at all pH.
  • Enhanced temperature stability These materials can be used at temperatures up to 250°C, preferably up to 200°C without significant degradation in performance.
  • a combination of different organic groups is possible. For instance, it is within the bounds of the present invention to attach more than one type of organic group to the same carbonaceous material or use a combination of carbonaceous materials, wherein some ofthe carbonaceous material has been modified with one organic group and another portion ofthe carbonaceous material has been modified with a different organic group. Varying degrees of modification are also possible, such as low weight percent or surface area modification, or a high weight percent or surface area modification. Also, mixtures of modified carbonaceous material and unmodified carbonaceous material can be used. Mixtures of modified carbonaceous material with different functionalizations and/or different levels of treatment can be used.
  • the modified carbonaceous materials of the present invention can be directly analogous to polymeric ion exchange resins.
  • These types of carbonaceous materials of the present invention can have one or more of the following properties as compared to conventional polymeric ion exchangers: a) higher temperature stability; b) greater resistance to swelling; and c) greater mechanical strength without adversely affecting uptake kinetics.
  • modified carbonaceous materials of the present invention besides being used as adsorbents, can also be used in separations ranging from water treatment to metals separation/recovery, ion exchange, catalysis, and the like.
  • An additional advantage of an adsorbent possessing exchangeable groups as described above is that it confers on the material the ability to be further surface modified using ion exchange procedures.
  • any adsorbate capable of being adsorbed by one or more of the modified carbonaceous materials ofthe present invention is contemplated to be within the bounds of the present invention.
  • examples include, but are not limited to, polar species such as water, ammonia, mercaptans, sulfur dioxide, and hydrogen sulfide.
  • polar species it is understood that this is a species whose electronic structure is not symmetrical. This includes molecules that possess dipole moments, for example H 0 and NH 3 ; and or molecules that possess quadrupole moments, such as CO2 and molecules that possess unsaturated pi bonds ( ⁇ ), such as alkenes, alkynes, and other organic and inorganic compounds with double and triple bonds.
  • Non-polar species such as argon, oxygen, methane, and the like can also be adsorbed with the appropriate modified carbonaceous materials of the present invention.
  • those skilled in the art will be able to determine which organic groups need to be attached to the carbonaceous materials in order to achieve the most effective adsorption affinity or increase in adsorption, depending upon the adsorbate and the adsorption processes involved.
  • an adsorbent composition containing a modified carbonaceous material capable of adsorbing an adsorbate By developing an adsorbent composition containing a modified carbonaceous material capable of adsorbing an adsorbate, selectivity for a particular adsorbate can be enhanced.
  • modifying the carbonaceous material to create the adsorbent composition of the present invention can decrease adsorption affinity for one component in order to maximize the adsorption affinity of another component which will maximize separation of the second component from the first component.
  • the carbonaceous material can be modified in such a manner as to add a hydrophobic group to "disable" the oxygen functionalities on the surface ofthe carbonaceous material to increase the selectivity for the adsorption of nonpolar species.
  • the adsorbate can be in a liquid phase or in the gaseous or vapor phase, depending upon the needs and desires ofthe user. Certain adsorbates can be more efficiently adsorbed from the vapor or gaseous phases than from the liquid phase or vice versa, and the modified carbonaceous materials ofthe present invention are effective in adsorption from either phase.
  • One advantage of the present invention is to modify the surface of an activated carbon or carbon black adsorbent extensively, without damaging the structure or making the adsorbent more friable.
  • a carbonaceous material can be surface modified based on the present invention with exchangeable sodium cations attached to the surface. This is very useful from the point of view of substituting different ions to alter the chemistry ofthe surface.
  • the beneficial effect of using the modified carbonaceous materials of the present invention for the purpose of adsorption can be demonstrated by comparing the adso ⁇ tion isotherms of an adsorbate on an unmodified carbonaceous adsorbent and the same carbonaceous adsorbent modified in accordance with the present invention.
  • the effectiveness of the surface modification of exemplary carbonaceous material was determined by comparing the adso ⁇ tion isotherms of various adsorbates on the unmodified carbonaceous materials, with adsorption isotherms on the carbonaceous materials modified in accordance with the present invention.
  • Adsorbates used were water and
  • Tahle 1 Surface Areas and Pore Volumes of Unmodified and Surface Modified Materials
  • both the carbon black and the activated carbon underwent an increase in adsorption capacity per unit surface area as a result ofthe surface modification.
  • the loss of any surface area and pore volume may be mitigated by pre-treating the carbonaceous material with immiscible organic solvent, like heptane.
  • the results from adso ⁇ tion of water vapor at 298 K on the unmodified and modified material are shown in Figure 1 (carbon black) and Figure 2 (activated carbon).
  • the water adso ⁇ tion experiments were carried out by a batch technique that involved equilibrating the sample with water vapor at a constant relative humidity, in a sealed cell.
  • the constant relative humidities were attained by using saturated salt solutions, which have known relative humidities above their surface.
  • Both the activated carbon and carbon black contained Na ions on the surface after the surface modification was carried out.
  • the Na ions can be substituted by other ions using standard ion exchange procedures (e.g., see Ion Exchange, by F. Helfferich, McGraw-Hill, 1962).
  • the water adsorption isotherms for the surface-modified material with Na ions on the surface, as well as the other ionic forms derived by ion exchange, are shown in Figures 1 and 2.
  • the adsorption isotherms show the quantity of water vapor adsorbed, per gram of adsorbent, as a function of the relative pressure of water vapor.
  • Figures 3 and 4 show the same data normalized by the BET surface area ofthe materials.
  • the surface modification technique ofthe present invention may affect the adso ⁇ tion of gases like C0 2 as well, which possesses a quadrupole movement.
  • Figure 5 shows the adso ⁇ tion isotherm of C0 2 from the gas phase at 273 K on the same unmodified and modified Black Pearls® 430 carbon black. Adso ⁇ tion of C0 2 was carried out on an ASAP 2000 automated adso ⁇ tion system manufactured by Micromeritics Co ⁇ . The figure shows the quantity of C0 2 adsorbed as a function of the CO 2 pressure. Clearly, the adsorption of C0 2 is enhanced by the carbon surface modification technique described in this invention.
  • Example 2 Example 2
  • the modified carbon blacks were dispersed in water during their preparation and subsequently purified by 10 volumes of diafiltration for removal of impurities and reaction byproducts.
  • a stock solution of 10 mg/ml of Bovine Serum Albumin (BSA) was prepared and used for all the experiments detailed below.
  • Appropriate amounts of dispersion containing 0.5 g of each modified carbon black and 0.5 g of unmodified BP3700 were introduced in separate 20 ml vials. In each vial, protein solution and deionized water were introduced so that the total final weight of the contents of each vial was approximately 7.5 g, with approximately 7 ml of liquid. Protein solutions varied in concentrations between 0 and 4.5 mg/ml.
  • the vials were vortexed for 2 hours to intimately mix the protein solution with the carbon black particles. After 1 week, the vials were vortexed again, and subsequently 2 ml aliquots were taken and centrifuged at -soi l, 000 RPM for the time required to separate the carbon black particles.
  • the protein concentrations in the supernatant solutions were measured using the standard Bradford assay. The protein concentrations were measured using the standard Bradford Assay as described in Analytical Biochemistry, 72, pp. 248-254 (1976), which is incorporated in its entirety by reference herein. As a comparison, Black Pearls® 3700 which was not modified was used as a control.
  • the remaining concentration of BSA in the aqueous solution was measured after 1 week and the amount of BSA adsorbed by the various carbonaceous materials in the separate experiments was plotted.
  • the modified carbonaceous material ofthe present invention was quite successful in not adsorbing the protein since the diagonal line in Fig. 6 represents no adso ⁇ tion and as can be seen, the chemically modified carbonaceous materials ofthe present invention were quite successful in not adsorbing significant amounts of proteins on the surface.
  • the untreated or conventional carbon black adsorbs significant amounts ofthe BSA on the carbon surface.
  • the present invention through the use of organic groups on a carbonaceous material can be quite successful in promoting non-specific adso ⁇ tion of protein at the carbon surface.
  • the particles were rinsed with ethanol, tetrahydrofuran (THF), and a 1 wt% NaOH solution and then soxhlet extracted for 16 hours in ethanol and 12 hours in THF.
  • the particles SP-1 were subsequently left to dry.
  • the starting particles ZirChrom-Carb particles had 1.18 wt% C and the final SP-1 particles had 3.4 wt%C, indicating surface coverage with octadecylphenyl groups.
  • SP-7 F.nd apping of octader.ylphenyl surface modified carbon-dad zirconia particles with t-hiitylph nyl groups
  • the particles SP-1 prepared in the previous step were mixed in a beaker with 22.5 g of deionized water, 7.5 g of ethanol, 0.22 g of 4-tert-butylaniline, and 0.63 g of a 30 wt% nitric acid solution and heated to 60 °C. 0.52 g of a 20 wt% solution of sodium nitrite were added dropwise over 2 minutes. The mixture was left to react at 60 °C for 1.5 hours.
  • the reaction mixture was left to cool to room temperature and filtered using Whatman 1 filter paper.
  • the particles were rinsed with ethanol, THF, and 1 wt% NaOH solution and extracted in ethanol for 16 hours and THF for 8 hours.
  • the particles SP-2 were subsequently left to dry.
  • the final particles had 3.72 wt%C indicating that tert-butylphenyl groups were attached to the surface.
  • Dodecylphenyl surface modified carbon-clad zirconia particles (SP-3) were prepared using a similar procedure to that described in Example 3 for the preparation of particles SP-1, using equivalent molar amounts of 4-dodecylaniline instead of 4- octadecylaniline as the treating reagent, t-butyl phenyl endcapped dodecylphenyl surface modified carbon-clad zirconia particles (SP-4) were also prepared starting from particles SP-3, using a procedure similar to that described in Example 3 for the preparation of particles SP-2 from particles SP-1.
  • lidocaine, atenolol, and labetalol were measured using HPLC columns packed with ZirChrom-Carb, particles SP-2, SP-3, and SP-4.
  • the solutes were injected in 5 ⁇ l volumes into a mobile phase consisting of 80 vol% acetonitrile and 20 vol% 20 mM potassium phosphate buffer at pH 10, held at 30 °C and flowing at 1 ml/min.
  • the retention factors are compared in Table 3.
  • Atenolol and labetalol are very strongly retained on the starting ZirChrom-Carb HPLC column, because their retention factors are greater than 30.
  • the particles were filtered by vacuum filtration and washed with THF and Ethanol and subsequently extracted for 3 hours with THF.
  • the starting particles ZirChrom-Carb particles had 1.68 wt% C and 0.05 wt% N and the final SP-6 particles had 3.1 wt% C and 0.33 wt%N.
  • the particles were rinsed with ethanol, THF, and a 1 wt% NaOH solution and then soxhlet extracted overnight in ethanol.
  • the particles SP-7 were subsequently left to dry.
  • the starting ZirChrom-Carb particles had 1.03 wt% C and the final SP-7 particles had 2.41 wt%C, indicating surface coverage with phenethylamino groups.

Abstract

La présente invention concerne des dispositifs et des systèmes de séparation qui ont une phase stationnaire et une phase mobile, ladite phase stationnaire contenant une matière carbonée à laquelle est attaché au moins un groupe organique. La phase stationnaire qui est utilisée dans la présente invention est capable de choisir sa sélectivité en fixant les groupes organiques appropriés sur la matière carbonée afin d'assurer la séparation désirée. Plusieurs processus de séparation sont décrits tels que la chromatographie, l'électrophorèse, les séparations magnétiques, les séparations par membranes et autres. Les processus permettant d'effectuer ces types de séparation sont également présentés.
EP01968422A 2000-09-01 2001-08-31 Chromatographie et autres procedes d'adsorption dans lesquels on utilise des adsorbants au carbone modifies Withdrawn EP1314026A2 (fr)

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