Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
  • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
  • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
  • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
  • C07C13/64—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings with a bridged ring system

Definitions

• This invention is directed to isolated or enriched higher diamondoid components and to compositions comprising one or more higher diamondoid components. This invention is also directed to novel methods for the separation and isolation of higher diamondoid components into recoverable fractions from a feedstock containing one or more higher diamondoid components.
• Diamondoids are hydrocarbon molecules possessing incredibly rigid structures that contain carbon atom frameworks that are superimposable on the diamond crystal lattice 1 (see FIG. 1).
• Adamantane a ten-carbon molecule, is the smallest member of the diamondoid series, consisting of one cage-shaped diamond crystal subunit.
• Adamantane is commercially available and is widely used as a chemical intermediate. It can be synthesized and it can be recovered from petroleum.
• Diamantane contains two face-fused diamond subunits and triamantane three. These three materials have been synthesized and isolated from petroleum and have received research attention.
• Adamantane, diamantane and triamantane are classified as "lower diamondoids”.
• Tetramantane, pentamantanes, etc. have characteristics (including multiple isomers, chirality and, above tetramantane, multiple molecular weight forms) that differ from the lower diamondoids, and are classified as "higher diamondoids". While only one of the higher diamondoids has been synthesized, ideas concerning their structures and hypothetical properties have been set forth.
• FIG. 2 is a table showing the different series of molecular weights calculated for higher diamondoids ranging from the tetramantanes to the undecamantanes.
• This invention provides higher diamondoids, as enriched or isolated compounds. It also provides the individual higher diamondoid isomers (referred to as "higher diamondoid components" as enriched or isolated compounds for the first time. In addition, this invention provides processes with which the enriched and isolated higher diamondoids and higher diamondoid components can be obtained.
• FIG. 1 illustrates the cage-shaped structure of diamondoids and their correlation to diamonds. Specifically illustrated is the correlation of the structures of diamondoids to subunits of the diamond crystal lattice.
• FIG. 2 is a table depicting the different molecular weights shown by each higher diamondoid series.
• FIG. 3 illustrates the stracture of the tetramantanes provided by this invention.
• FIG. 4 illustrates that the four tetramantanes have carbon frameworks that correlate with the diamond lattice and can be viewed into their 100 lattice plane (FIG. 4A), 110 lattice plane (FIG. 4B) and 111 diamond lattice plane (FIG. 4C).
• FIG. 5 illustrates the structure of the pentamantanes provided by this invention.
• FIG's. 6A, 6B, 6C and 6D illustrate the stracture of the hexamantanes provided by this invention.
• FIG's. 7 A, 7B and 7C illustrate the stracture of the heptamantanes provided by this invention. Only one of each enantiomer is shown.
• FIG. 8 illustrates the structure of the octamantanes provided by this invention. Only examples of the 500, 486, 472 and 432 molecular weight forms are shown.
• FIG. 9 illustrates the stracture of the nonamantanes provided by this invention. Only examples of each molecular weight family are shown.
• FIG. 10 illustrates the stracture of the decamantanes provided by this invention.
• FIG. 11 illustrates the stracture of the undecamantanes provided by this invention. Only examples of each molecular weight family are shown.
• FIG. 12 gives a flow chart representing the various steps used in the isolation of higher diamondoid-containing fractions and individual higher diamondoid components.
• FIG's. 13 A and 13B are compilations of the GC/MS and HPLC properties of various higher diamondoids included in this application.
• FIG. 14 shows the two-HPLC column strategy used to isolate individual tetramantanes and pentamantanes.
• FIG. 15 illustrates the size and shape of selected higher diamondoids relative to
• C 60 (Buckminsterfullerene) and a representative carbon nanotube used in the development of molecular electronic devices.
• the carbon framework structures of the selected diamondoids can be found in FIG's 5, 6, 8, 9 and 10.
• FIG. 16 illustrates the gas chromatogram of a gas condensate feedstock; one of the original feedstocks used in the Examples (Feedstock A); showing minute concentrations of higher diamonds (not detectable on this scale).
• FIG. 17 illustrates a high temperature simulated distillation profile of Feedstock B using the atmospheric distillation 650 °F + bottoms as feedstock. This figure also illustrates the targeted cut points (1-10) we used for higher diamondoid isolations.
• FIG' s. 18 A and 18B illustrate gas chromatograms (FID) of distillate fraction #6
• FIG's. 19 and 20 are charts illustrating elution sequences for a variety of individual higher diamondoids (hexamantanes) on two different HPLC chromatography columns: ODS and Hypercarb as discussed in Examples 1 and 7.
• FIG's. 21A and 21B illustrate the preparative capillary gas chromatographic data for tetramantane isolations carried out in Examples 3 and 5.
• FIG. 21A shows cuts made on distillate fraction #33, Feedstock A.
• the bold face numbers refer to peaks of the tetramantanes.
• FIG. 21B shows peaks isolated and sent to the traps.
• the circled numbered peaks (2, 4, and 6) are the tetramantanes. It is noted that both enantiomers of the optically- active tetramantane are contained within one of these peaks.
• FIG. 22A, 22B and 22C illustrate photomicrographs of tetramantane crystals isolated from Feedstock A by preparative gas chromatography (FIG. 21).
• FIG. 22A was isolated from trap fraction #2
• FIG. 22B was isolated from trap fraction #4
• FIG. 22C was isolated from trap fraction #6. Because the two enantiomeric tetramantanes have identical GC retentions times in FIG. 21, one of the crystals contains both enantiomers.
• FIG. 23 A illustrates the gas chromatogram of Feedstock B atmospheric distillation hold up fraction, exemplified in Example 1, which was used as feedstock in pyrolytic processing.
• the hold up fraction is the material recovered from the distillation column after distillation of Feedstock B at approximately 650°F. Tetramantanes #1 to #3 are shown.
• FIG. 23B illustrates the gas cliromatogram of the pyrolytic product from the starting material in FIG. 23 A, i.e. the holdup fraction of Feedstock B atmospheric distillation 650 °F + bottoms, showing the degradation of non-diamondoid components.
• FIG. ' s 24A and 24B compare the gas chromatograms of a tetramantane- containing starting mixture injected into a Vydac ODS HPLC column, and HPLC cut #6 enriched in a tetramantane component.
• FIG. 25 illustrates a preparative ODS HPLC isolation of the holdup fraction of Feedstock B atmospheric distillation 650 °F + bottoms, showing fractions taken at various retention times and the elution order of the tetramantane components and the location time of fraction #12 used in subsequent isolations steps.
• FIG. 23 above displays the gas chromato graph of this feedstock.
• FIG. 26 illustrates the HPLC chromatogram of fraction 12 (FIG. 25) run on Hypercarb stationary phase with acetone mobile phase resulting in the isolation of tetramantane #2.
• FIG' s. 27A and 27B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of tetramantane #1 isolated by using two different HPLC columns.
• FIG's. 28 A and 28B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of tetramantane #2 isolated by using two different HPLC columns.
• FIG's. 29A and 29B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of tetramantane #3 isolated by using two different HPLC columns.
• FIG's. 30A and 30B show the GC/MS total ion chromatogram (TIC) and mass spectrum of a methyltetramantane isolated using Hypercarb HPLC.
• FIG's. 31 A and 3 IB illustrate a preparative capillary gas chromatographic data for pentamantane isolations.
• FIG. 31 A shows the first column cut containing one of the pentamantanes from thermally treated Feedstock B. The material in that cut was separated on a second column.
• FIG. 3 IB shows the second column peak sent to the trap.
• Pentamantane #1 the first pentamantane to elute in GC/MS analysis, was isolated in trap 6.
• FIG's. 32A and 32B show the GC/MS total ion chromatogram and mass spectrum of pentamantane #1 isolated by preparative capillary gas chromatography.
• FIG. 33A is a photomicrograph of pentamantane #1 crystals isolated from Feedstock B by preparative gas chromatography (FIG. 31 and 32).
• FIG. 33B illustrates a pentamantane co-crystal.
• FIG. 34 illustrates the preparative HPLC Refractive Index trace (with negative polarity) of Feedstock B distillate cut pyrolysis product saturated hydrocarbon fraction showing HPLC fractions taken using octadecyl silane columns and acetone mobile phase. Pentamantanes are numbered in order of their elution on the GC/MS analyses.
• FIG. 35 illustrates the chromatogram of ODS HPLC fraction 11 (FIG. 34) run on Hypercarb stationary phase with acetone mobile phase resulting in the isolation of pentamantane #1.
• FIG' s. 36 A and 36B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #1 isolated using two different HPLC columns.
• FIG's. 37A and 37B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #2 isolated using two different HPLC columns.
• FIG's. 38A and 38B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #3 isolated using two different HPLC columns.
• FIG's. 39A and 39B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #4 isolated using two different HPLC columns.
• FIG's. 40A and 40B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #5 isolated using two different HPLC columns.
• FIG's. 41A and 41B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #6 isolated using two different HPLC columns.
• FIG's. 42A and 42B illustrate the preparative capillary gas chromatographic data for hexamantane isolations.
• FIG. 42 A shows the first column cuts containing two of the hexamantanes from Feedstock B.
• FIG. 42B shows the second column peaks isolated and sent to the traps. From this procedure pure hexamantanes were isolated (FIG.'s 43 and 44), hexamantane #2, the second hexamantane to elute in our GC/MS assay, while hexamantane #8 is the eighth to elute.
• FIG's. 43 A and 43B illustrate the GC/MS total ion chromatogram and mass spectrum of a hexamantane #2 isolated by preparative capillary gas chromatography.
• FIG's. 44A and 44B illustrate the GC/MS total ion chromatogram and mass spectrum of a hexamantane #8 highly concentrated by preparative capillary gas chromatography. A minor amount of a methylheptamantane (408 molecular weight) is present in this sample.
• FIG. 45 illustrates a photomicrograph of hexamantane #2 crystals isolated from Feedstock B by preparative gas chromatography (FIG. 42 and 44).
• FIG. 46 illustrates a photomicrograph of hexamantane #8 crystals isolated from Feedstock B by preparative gas chromatography (FIG. 145 and 147).
• FIG's. 47A and 47B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #8 in ODS HPLC fraction #39.
• FIG's. 48A and 48B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #10 in ODS HPLC fraction #48.
• FIG's. 49A and 49B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #6 in ODS HPLC fraction #63.
• FIG's. 50A and 50B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane # 2 greatly enriched in Hypercarb HPLC fraction #53.
• FIG's. 51 A and 5 IB illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane # 13 isolated using two different HPLC columns.
• FIG's. 52A and 52B illustrate GC MS total ion chromatogram (TIC) and mass spectrum of hexamantane # 7 isolated using two different HPLC columns.
• FIG's. 53A and 53B illustrate GC/MS reconstructed ion chromatogram m/z 382 and mass spectrum of a condensed "irregular" hexamantane (mol. wt. 382) in the saturated hydrocarbon fraction of the product of the pyrolytic processing of Feedstock B distillation fraction #6.
• FIG's. 54A and 54B illustrate GC/MS reconstracted ion chromatogram m/z 382 and mass spectrum of an irregular hexamantane (mol. wt. 382) in the ODS HPLC fraction
• FIG's. 55A and 55B illustrate GC MS total ion chromatogram (TIC) and mass spectrum of a methylhexamantane (mol. wt. 410) isolated in ODS HPLC fraction #55.
• FIG. 56 illustrates GC/MS total ion chromatogram (TIC) of cyclohexamantane and methylcyclohexamantane-containing ODS HPLC combined fractions #23-26.
• FIG's. 57A and 57B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of a methylcyclohexamantane #1 (mol. wt. 356) isolated using multi-column stationary phase HPLC (ODS followed by Hypercarb).
• FIG's. 58A and 58B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of a methylcyclohexamantane #2 (mol. wt. 356) isolated in high purity using multi- column stationary phase HPLC (ODS followed by Hypercarb).
• FIG's. 59 and 60 show photomicrographs of crystals of methylcyclohexamantane #1 and methylcyclohexamantane #2 isolated using two different
• FIG's. 61 A and 61B illustrate the preparative capillary gas chromatographic data for heptamantane isolations.
• FIG. 61 A shows the first column cuts containing two of the heptamantanes from Feedstock B.
• FIG. 61B shows the second column peaks isolated and sent to the traps. From this procedure pure heptamantane components were isolated (FIG 8 and 9) , heptamantane #1, the first heptamantane to elute in our GC/MS assay, and heptamantane #2 which is the second to elute.
• FIG's. 62A and 62B illustrate the GC/MS total ion chromatogram and mass spectrum of a heptamantane #1 isolated by preparative capillary gas chromatography.
• FIG's. 63A and 63B illustrate the GC/MS total ion chromatogram and mass spectrum of a heptamantane #2 highly concentrated by preparative capillary gas chromatography.
• FIG. 64 illustrates photomicrographs of heptamantane #1 crystals isolated from
• Feedstock B by preparative gas chromatography (FIG's. 61 and 62).
• FIG. 65 illustrates a photomicrograph of heptamantane #2 crystals isolated from Feedstock B by preparative gas chromatography (FIG's. 61 and 63).
• FIG's. 66A and 66B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane component #1 in ODS HPLC fraction #45.
• FIG' s. 67A and 67B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane component #2 in ODS HPLC fraction #41.
• FIG's. 68 A and 68B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane component #9 in ODS HPLC fraction #61.
• FIG' s. 69A and 69B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane component #10 in ODS HPLC fraction #87.
• FIG's. 70A and 70B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane # 1 greatly enriched in Hypercarb HPLC fraction #55.
• FIG's. 71 A and 71B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane #2 isolated using two different HPLC columns. Heptamantane #2 was isolated from ODS HPLC fraction #41 (FIG. 67) using the Hypercarb HPLC system.
• FIG. 72 illustrates GC/MS reconstructed ion chromatogram m/z 420 showing a partially condensed heptamantane component (mol. wt. 420) in the ODS HPLC fraction #61.
• FIG. 73 illustrates the mass spectrum of the molecular weight 420 heptamantane in FIG. 72.
• FIG' s. 74 A and 74B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of a methylheptamantane component (mol. wt. 408) isolated in ODS HPLC fraction #51.
• FIG's. 75 A and 75B illustrate the GC/MS total ion chromatogram and mass spectrum of octamantane #1 highly concentrated by high performance liquid chromatography.
• FIG. 76 illustrates a photomicrograph of octamantane #1 crystals isolated from Feedstock B by high performance liquid chromatography.
• FIG's. 77A and 77B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of co-crystalline octamantane #3 and octamantane #5 (FIG. 78) grown from ODS HPLC fraction #63.
• TIC total ion chromatogram
• FIG's. 78 A and 78B illustrate photomicrographs of co-crystalline octamantane #3 and #5, crystal B was dissolved in cyclohexane and analyzed by GC/MS (FIG. 77).
• FIG's. 79A and 79B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of octamantane #1 and octamantane #10 containing ODS HPLC fraction #80.
• FIG's. 80A and 80B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of an octamantane (molecular weight 500)-containing ODS HPLC fraction #92.
• FIG's. 81 A and 8 IB illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of a methyloctamantane (mol. wt. 460) in ODS HPLC fraction #94.
• FIG' s. 82 A and 82B illustrate the GC/MS total ion chromatogram and mass spectrum of a nonamantane concentrated by high performance liquid chromatography.
• FIG's. 83A and 83B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of a nonamantane concentrated using two different HPLC columns.
• FIG's. 84A and 84B illustrate a photomicrograph of a nonamantane crystal and a mass spectra of the dissolved crystal.
• FIG's. 85A and 85B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of a methylnonamantane (mol. wt. 512).
• FIG's. 86A and 86B illustrate the GC/MS total ion chromatogram and mass spectrum of [1231241(2)3], molecular weight 456, decamantane concentrated by high performance liquid chromatography.
• FIG's. 87A and 87B illustrate GC/MS total ion chromatogram (TIC) and mass spectrum of [1231241(2)3], molecular weight 456, decamantane isolated using two different HPLC columns.
• FIG's. 88A and 88B illustrate a photomicrograph of [1231241(2)3], molecular weight 456, decamantane crystal and a mass spectra of the dissolved crystal.
• FIG's. 89A and 89B illustrate GC/MS selected ion chromatogram (TIC) and mass spectrum of a decamantane (mol. wt. 496).
• FIG's. 90A and 90B illustrate GC/MS total ion chromatogram (TIC) of two methyldecamantanes (mol. wt. 470), and the mass spectrum of the one eluting at 18.84 min. in the GC/MS analysis.
• TIC total ion chromatogram
• FIG's. 91 A and 9 IB illustrate illustrates the GC/MS selective ion chromatogram (m z 508) and mass spectrum of pyrolysis product of Feedstock B atmospheric distillation fraction #7 (Table 3) concentrating undecamantanes.
• FIG's. 92A, 92B and 92C illustrate a GC/MS selected ion chromatogram (m/z 508) and mass spectrum of an undecamantane component (mol. wt. 508) eluting at 21.07 min. and the mass spectrum of a methylundecamantane component (mol. wt. 522) eluting at 21.30 min.
• FIG. 93 is a chart illustrating distillation cuts of a higher diamondoid-containing feedstock (Feedstock B, atmospheric distillation residue) showing cut selections to favor the enrichment of specific groups of higher diamondoids.
• FIG. 94 shows the screw-like structures (right and left-handed) of [12341] hexamantane.
• diamondoid refers to substituted and unsubstituted caged compounds of the adamantane series including adamantane, diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, undecamantane, and the like and also including all isomers and stereoisomers thereof.
• Substituted diamondoids preferably comprise from 1 to 10 and more preferably 1 to 4 alkyl substituents.
• lower diamondoid components or “adamantane, diamantane and triamantane components” refers to any and/or all unsubstituted and substituted derivatives of adamantane, diamantane and triamantane.
• higher diamondoid components refers to any and/or all substituted and unsubstituted diamondoids corresponding to tetramantanes and above including tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes, nonamantanes, decamantanes, undecamantanes, and the like including all isomers and stereoisomers thereof.
• the higher diamondoids include substituted and unsubstituted tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes, nonamantanes, decamantanes and undecamantanes.
• FIG. 2 is a Table which shows representative higher diamondoids together with their molecular weights.
• the terms "diamondoid family”, “tetramantane family” and the like are used to define a group of like “diamondoid components", having the same number of diamond crystal lattice cage units.
• tetramantane components refer to any and/or all substituted and unsubstituted diamondoids corresponding to tetramantane.
• pentamantane components refer to any and/or all substituted and unsubstituted diamondoids corresponding to pentamantane.
• non-ionized diamondoid components refers to higher diamondoid components which do not carry a charge such as a positive charge generated during mass spectral analysis wherein the phrase “higher diamondoid components” is as defined herein.
• non-ionized tetramantane components refers to tetramantane components which do not carry a charge such as a positive charge generated during mass spectral analysis.
• non-ionized pentamantane components and diamondoid components higher than pentamantane refers to pentamantane components and higher diamondoid components larger than pentamantane which do not carry a charge such as a positive charge generated during mass spectral analysis.
• selected higher diamondoid components refers to one or more substituted or unsubstituted higher diamondoids that are desired to be isolated or “enriched” in a product.
• nonselected higher diamondoid components and the like refer to those higher diamondoids that are not “selected higher diamondoids”.
• enriched when used to describe the state of purity of one or more higher diamondoid components refers to such materials at least partially separated from the feedstock, and in the case of "enriched” individual higher diamondoid components, concentrated at least 25 and preferably at least 100 times the original concentration exhibited in the feedstock.
• enriched higher diamondoid or “enriched” higher diamondoid components make up at least 25%, especially at least 50% (i.e., 50-100%), more preferably at least 75% and yet more preferably at least 95% or even at least 99% by weight of the overall material in which they are present or in other words exhibit a weight purity of at least
• feedstock or "hydrocarbonaceous feedstock” refers to hydrocarbonaceous materials comprising recoverable amounts of higher diamondoids.
• feedstocks include oil, gas condensates, refinery streams, oils derived from reservoir rocks, oil shale, tar sands, and source rocks, and the like.
• Such components typically, but not necessarily, comprise one or more lower diamondoid components as well as non-diamondoid components. The latter is typically characterized as comprising components having a boiling point both below and above the lowest boiling point tetramantane which boils at about 350°C at atmospheric pressure.
• Typical feedstocks may also contain impurities such as sediment, metals including nickel, vanadium and other inorganics. They may also contain heteromolecules containing sulfur, nitrogen and the like. All of these nondiamondoid materials are included in "nondiamondoid components" as that term is defined herein.
• nonselected materials refers to the collection of feedstock components that are not “selected higher diamondoids” and include “nondiamondoid components", “lower diamondoids” and “nonselected higher diamondoid” as these terms are defined herein.
• the term "remove” or “removing” refers to processes for removal of nondiamondoid components and/or lower diamondoid components and/or nonselected higher diamondoid components from the feedstock. Such processes include, by way of example only, size separation techniques, distillation, evaporation either under normal or reduced pressure, well head separators, sorption, chromatography, chemical extraction, crystallization and the like. For example, Chen, et al. 4 disclose distillation processes for removing adamantane, substituted adamantane, diamantane, substituted diamantane, and triamantane from a hydrocarbonaceous feedstock.
• distillation or “distilling” refers to the fractionation processes in which materials are separated based on differences in vapor pressures, with high vapor pressure materials being taken overhead. Distillation can be carried out on hydrocarbonaceous feedstocks and on fractions otherwise obtained during the processing of hydrocarbonaceous feedstocks. In this context, most commonly, distillations are conducted under vacuum but also could be at atmospheric or even elevated pressures.
• fractionation and “fractionating” refer to processes in which materials in a mixture are separated from each other such as by differential solubility, differential vapor pressure, differential chromatographic affinity and the like.
• pyrolysis and “thermal treating to pyrolyze” and the like refer to either atmospheric, reduced pressure or elevated pressure heating of the feedstock or a feedstock fraction to thermally degrade a portion of one or more components in the feedstock.
• non-diamondoid components of a feedstock refers to components of the feedstock or a feedstock fraction which are not diamondoid in character wherein the term
• the term "retained” refers to retention of at least a portion of the higher diamondoid components found in the recovered feedstock when compared to the amount of such diamondoids found in the original feedstock.
• at least about 10 weight percent of the higher diamondoid components are retained in the recovered feedstock; more preferably, at least about 50 weight percent of the higher diamondoid components are retained in the recovered feedstock; and still more preferably, at least about 90 weight percent of the higher diamondoid components are retained in the recovered feedstock; each based on the total amount of such diamondoids found in the feedstock prior to treatment.
• alkyl refers to straight and branched chain saturated aliphatic groups typically having from 1 to 20 carbon atoms, more preferably 1 to 6 atoms ("lower alkyls”), as well as cyclic saturated aliphatic groups typically having from 3 to 20 carbon atoms and preferably from 3 to 6 carbon atoms ("lower alkyls" as well).
• alkyl and “lower alkyl” are exemplified by groups such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, t-butyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
• higher diamondoids are bridged-ring cycloalkanes that have carbon-atom frameworks that can be superimposed on the diamond crystal lattice (FIG's. 1 and 4). They are the tetramers, pentamers, hexamers, heptamers, octamers, nonamers, decamers, etc. of adamantane (tricyclo[3.3.1.1 3 ' 7 ]decane) or C ⁇ 0 H ⁇ 6 in which various adamantane units are face-fused.
• the higher diamondoids can contain many alkyl substituents. These compounds have extremely rigid stractures and have the highest stability of any compound with their formula. There are four tetramantane structures (FIG's. 2 and
• FIG. 3 tso-teframantane [1(2)3], ⁇ ntz-tetramantane [121] and two enantiomers of skew- tetramantane [123] (FIG. 3) with the more general bracketed nomenclature for these diamondoids in accordance to a convention by Balaban et al. 15
• pentamantanes FIG. 5
• nine have the molecular formula C 26 H 3 (molecular weight 344), and among these nine there are three pairs of enantiomers represented by: [12(1)3], [1234], [1213] with the non-enantiomeric pentamantanes represented by: [12(3)4], [1(2,3)4], [1212].
• Heptamantanes are postulated to exist in one hundred and sixty possible structures; with eighty-five having the molecular formula C H 0 (molecular weight 448) (FIG. 7) and of these, seven are achiral, having no enantiomers.
• octamantanes eighteen have the molecular formula C 34 H 38 (molecular weight 446).
• FIG. 8 show ⁇ s each of the 446 molecular weight octamantane isomers.
• Other octamantanes have the molecular formula C 38 H (molecular weight 500).
• the remaining octamantane families, C 37 H 42 (molecular weight 486), C 6 H 40 (molecular weight 472) and C 33 H 36 (molecular weight 432) show greater bond strain and correspondingly lower stability.
• Nonamantanes exist within six families of different molecular weights having the following molecular formulas: C 42 H 48 (molecular weight 552), C 41 H 46 (molecular weight 538), C 0 H 4 (molecular weight 524), C ⁇ I ⁇ (molecular weight 498), C 37 H4o (molecular weight 484) and C 34 H 36 (molecular weight 444). Additionally, decamantane exists within families of seven different molecular weights. Among the decamantanes, there is a single decamantane having the molecular formula C 35 H 3 (molecular weight 456) which is structurally compact in relation to the other decamantanes and has low internal bond strain.
• decamantane families have the molecular formulas: C 46 H 2 (molecular weight 604), C 45 H 5 o (molecular weight 590), C 44 H 48 (molecular weight 576), C 4 FJU 6 (molecular weight 550), C ⁇ H t4 (molecular weight 536) and C 38 H 40
• a feedstock is selected such that said feedstock comprises recoverable amounts of one or more selected higher diamondoid components.
• such feedstock comprises at least about 1 ppb of one or more higher diamondoid components, more preferably, at least about 25 ppb and still more preferably at least about 100 ppb. It is understood, of course, that feedstocks having higher concentrations of higher diamondoid components facilitate recovery of these components.
• Preferred feedstocks include, for example, natural gas condensates and refinery streams having high concentrations of higher diamondoids.
• refinery streams include hydrocarbonaceous streams recoverable from cracking processes, distillations, coking and the like.
• Particularly preferred feedstocks include gas condensates recovered from the Norphlet Formation in the Gulf of Mexico and from the LeDuc Formation in Canada.
• the feedstocks used in the processes of this invention typically comprise non-diamondoid components having boiling points both below and above the lowest boiling point higher diamondoid component selected for recovery as well as one or more lower diamondoid components.
• These feedstocks will usually contain a mixture of higher diamondoids. Depending upon which higher diamondoids are selected, some of these higher diamondoids may have boiling points below the selected higher diamondoid' s boiling point. Typically, the lowest boiling point higher diamondoid component selected for recovery will have a boiling point of greater than about 335°C.
• the concentration of lower diamondoids to higher diamondoids is generally about 250:1 or higher.
• typical feedstocks comprising higher diamondoid components also comprise non-diamondoid components.
• the processes of this invention may entail removal of a sufficient amount of these contaminants from the feedstock under conditions to provide a treated feedstock from which the selected higher diamondoid components can be recovered.
• the removal of contaminants includes distillation of the feedstock to remove non-diamondoid components as well as lower diamondoid components and in some cases other nonselected higher diamondoids having boiling points less than that of the lowest boiling point higher diamondoid component selected for recovery.
• the feedstock is distilled to provide cuts above and below about 335°C, atmospheric equivalent boiling point and, more preferably, above and below about 345 °C atmospheric equivalent boiling point.
• the lower cuts which are enriched in lower diamondoids and low boiling point non-diamondoid components are taken overhead and discarded and the higher boiling cut, which is enriched in higher diamondoids, is retained.
• the temperature for the cut point during distillation is a function of pressure and that the above temperatures are referenced to atmospheric pressure. A reduced pressure will result in a lower distillation temperature to achieve the same cut point whereas an elevated pressure will result in a higher distillation temperature to achieve the same cut point.
• the correlation of pressure/temperature from atmospheric distillation to either reduced pressure or elevated pressure distillation is well within the skill of the art.
• Distillation can be operated to fractionate the feedstocks and provide several cuts in a temperature range of interest to provide the initial enrichment of the selected higher diamondoids or groups of selected higher diamondoids.
• the cuts which are enriched in one or more selected diamondoids or a particular diamondoid component of interest, are retained and may require further purification.
• the following Table illustrates representative fractionation points that may be used to enrich various higher diamondoids in overheads. In practice it may be advantageous to make wider temperature range cuts which would often contain groups of higher diamondoids which could be separated together in subsequent separation steps.
• substituted higher diamondoids may accordingly shift these preferred cut-point temperatures to higher temperatures due to the addition of substituent groups. Additional temperature refinements will allow for higher purity cuts for the diamondoid of interest.
• FIG. 93 provides further illustrations of how fractionation can provide cuts enriched in individual or multiple higher diamondoid components.
• fractionation can be stopped before a selected higher diamondoid is taken overhead. In this case the higher diamondoid can be isolated from the fractionation bottoms.
• Other processes for the removal of lower diamondoids, unselected higher diamondoids, if any, and/or hydrocarbonaceous non-diamondoid components include, by way of example only, size separation techniques, evaporation either under normal or reduced pressure, crystallization, chromatography, well head separators, reduced pressure and the like. Removal processes can utilize the larger sizes of the higher diamondoids to effect separation of lower diamondoids therefrom.
• size separation techniques using membranes will allow a feedstock retained in the membrane to selectively pass lower diamondoids across the membrane barrier provided that the pore size of the membrane barrier is selected to differentiate between compounds having the size of higher diamondoid components as compared to lower diamondoid components.
• the pore size of molecular sieves such as zeolites and the like can also be used to effect size separation.
• the removal process provides for a treated feedstock having a ratio of lower diamondoid components to higher diamondoid components of no greater than 9:1; more preferably, no greater than 2:1; and even more preferably, the ratio is no greater than 1:1. Even more preferably, after removal of the lower diamondoid component(s) from the feedstock, at least about 10%, more preferably at least 50% and still more preferably at least 90% of the higher diamondoid components are retained in the feedstock as compared to that amount found in the feedstock prior to the removal.
• the feedstock When recovery of hexamantane and higher diamondoid components is desired and when the feedstock contains non-diamondoid contaminants, the feedstock will also be generally subjected to pyrolysis to effect removal of at least a portion of the hydrocarbonaceous non-diamondoid components from the feedstock.
• the pyrolysis effectively concentrates the amount of higher diamondoids in the pyrolytically treated feedstock thereby rendering their recovery possible (FIG. 18).
• Pyrolysis is effected by heating the feedstock under vacuum conditions or in an inert atmosphere, at a temperature of at least about 390°C and, preferably, from about 400 to about 550°C, more preferably from about 400 to about 450°C , and especially 410 to 430°C; for a period of time to effect pyrolysis of at least a portion of the non-diamondoid components of the feedstock.
• the specific conditions employed are selected such that recoverable amounts of selected higher diamondoid components are retained in the feedstock. The selection of such conditions is well within the skill of the art.
• pyrolysis is continued for a sufficient period and at a sufficiently high temperature to thermally degrade at least about 10% of the non-diamondoid components (more preferably at least about 50% and even more preferably at least about 90%) from the pyrolytically treated feedstock based on the total weight of the non- diamondoid components in the feedstock prior to pyrolysis.
• At least about 10%), more preferably at least about 50%, and still more preferably at least about 90% of the higher diamondoid components are retained in the feedstock after pyrolytic freatment compared to that amount found in the feedstock prior to pyrolytic treatment.
• removal of lower diamondoids and low boiling point hydrocarbonaceous non-diamondoid components from the feedstock precedes pyrolytic treatment.
• pyrolytic treatment it is understood, that the order of these procedures can be inverted such that pyrolysis occurs prior to removal of lower diamondoids from the feedstock.
• the pyrolysis procedure while a preferred embodiment, is not always necessary. This arises because the concentration of higher diamondoids can be sufficiently high in certain feedstocks that the treated feedstock (after removal of the lower diamondoid components) can be used directly in purification techniques such as chromatography, crystallization, etc. to provide higher diamondoid components. However, when the concentration or purity of higher diamondoid components in the feedstock is not at the level to effect such a recovery, then a pyrolytic step should be employed.
• the recovered feedstock is first subjected to gravity column chromatography using silver nitrate impregnated silica gel followed by
• separation of enantioneric forms of the high diamondoids can be achieved using several approaches.
• One such approach is spontaneous crystallization with resolution and mechanical separation.
• This approach to enantiomer resolution can be enhanced by preparation of derivatives or by the use of additives, chiral solvents, or various types of seed crystals.
• Another resolution option is chemical separation under kinetic or thermodynamic control.
• Other suitable processes for enantiomer resolution include chiral separations, which can be performed using a gas chromatographic (GC) see "Chiral Chromatography", T.E. Beesley, et.
• GC gas chromatographic
• the processes of this invention provide compositions enhanced in higher diamondoids. These higher diamondoids are useful in micro- and molecular-electronics and nanotechnology applications. In particular, the rigidity, strength, stability, thermal conductivity, variety of structural forms and multiple attachment sites shown by these molecules makes possible accurate construction of robust, durable, precision devices with nanometer dimensions.
• FIG. 15 shows the size and shapes of selected higher diamondoids relative to molecular components (Buckminsterfullerene and carbon nanotubes) employed in the development of molecular electronic devices.
• the higher diamondoids are three-dimensional nanometer-sized units showing different diamond lattice arrangements. This translates into a great variety of shapes and sizes of these extremely rigid nanostractures, for example, [121(3)4] hexamantane is "T” shaped, [12134] is “L” shaped, and [1(2)3(1)2] is flat with four lobes. [12(3,4)12] heptamantane has a cross-shaped structure while [121234] is "L” shaped. [12312] hexamantane has a disc-like stracture.
• heptamantane is disc-shaped with one co- planar lobe, while [1213(1)21] octamantane is disc-shaped with two, opposing, co-planar lobes.
• octamantane is wedge-shaped.
• nonamatane has a triangular plate-like structure.
• decamantane is a perfect octagon, while [121231212] decamantane is rectangular plate-like stracture.
• undecamantane is an elongated pyramid.
• Higher diamondoids also include a series of rod-like stractures of varying lengths.
• the tetramantane with the sequence "121" is the first member of this rod-shaped structural series, [1212] pentamantane is next, followed by [12121] hexamantane, and so on.
• Each added diamond cage increases the length of the rod by about 0.3 nm, with [1212] pentamantane having a length of about 1.1 nm.
• Higher diamondoids also include screw-like structures of varying lengths.
• the first chiral diamondoid is the tetramantane with sequence 123.
• Their structures can also be implied by the sequences 123 and 124 by a modification of the Balaban nomenclature.
• These two diamondoids have left (counter-clockwise), i.e., tetramantane A, and right (clockwise) (tetramantane B)-hand helix or screw-like structures, both representing a partial-turn of the helix.
• Balaban nomenclature does not provide a way of specifying the left and right helical forms, only demonstrating that there exists two forms.
• This sequence continues with the progression 1234 and 1243 (i.e., A and B) for pentamantane (FIG. 5),
• the higher diamondoids may be used as novel materials of construction with special chemicals, optical, electric and thermal conductivity properties for coatings, film layering and other applications taking advantage of the diamond-like properties, etc.
• Novel uses of higher diamondoid- containing materials in the field of microelectronics are disclosed.
• Embodiments include, but not limited to, thermally conductive films in integrated circuit packaging, low-k dielectric layers in integrated circuit multilevel interconnents, thermally conductive adhesive films, thermally conductive films in thermoelectric cooling devises, passivation films for integrated circuit devices (ICs), and field emission cathodes.
• these higher diamondoids can also be used in a high quality lubricating fluid which exhibits a high Viscosity Index and a very low pour point. 13 When so employed, these fluids comprise a fluid of lubricating viscosity and from about 0.1 to 10 weight percent diamondoids.
• these higher diamondoids can be used as high density fuels in the manner described by Chung, et al. 14 , incorporated herein by reference.
• VLT vapor line temperature
• Example 1 describes a most universal route for isolating higher diamondoids components which can be applied to all feedstocks. This process uses HPLC (Step 7, FIG.
• Example 2 describes a variation of the process of Example 1 in which preparative gas chromatography (Step 1', FIG. 12) replaces HPLC as the final isolation step.
• Example 3 describes a variation of the process of Example 1 in which the pyrolysis (Step 5, FIG. 12) is omitted. As shown optionally in FIG. 12, the liquid chromatographic step (Step 6, FIG. 12) is also omitted.
• These variations generally have applicability only with selected feedstocks and generally when tetramantanes, pentamantane and cyclohexamantane are the target higher diamondoids.
• Example 4 describes yet another process variation in which the final products of Examples 1 and 3 are subjected to preparative gas chromatography purification to give further separation of higher diamondoid components (Step 8, FIG. 12).
• Example 5 describes the enrichment and isolation of the tetramantane components.
• Example 6 describes the enrichment and isolation of the pentamantane components.
• Example 7 describes the enrichment and isolation of the hexamantane components.
• Example 8 describes the enrichment and isolation of the heptamantane components.
• Example 9 describes the enrichment and isolation of the octamantane components.
• Example 10 describes the enrichment and isolation of the nonamantane components.
• Example 11 describes the enrichment and isolation of the decamantane components.
• Example 12 describes the enrichment and isolation of the undecamantane components. [000195] It will be understood that it is possible to vary the order of the various distillation, chromatography and pyrolysis steps, although the order set forth in Example 1 has given the best results.
• This Example has seven steps (see Flow Chart in FIG. 12).
• Step 1 Feedstock selection [000198] Step 2. GCMC assay development [000199] Step 3. Feedstock atmospheric distillation
• Step 6 Removal of aromatic and polar nondiamondoid components [000203]
• Step 7. Multi-column HPLC isolation of higher diamondoids a) First column of first selectivity to provide fractions enriched in specific higher diamondoids.
• Step 1 Feedstock Selection
• Suitable starting materials were obtained. These materials included a gas condensate, Feedstock A (FIG. 16), and a gas condensate containing petroleum components, Feedstock B. Although other condensates, petroleums, or refinery cuts and products could have been used, these two materials were chosen due to their high diamondoid concentration, approximately 0.3 weight percent higher diamondoids, as determined by GC and GC/MS. Both feedstocks were light colored and had API gravities between 19 and 20° API.
• FIG. 13 A is a table that lists typical GC/MS assay information for the hexamantanes (GC retention times, mass spectral molecular ion (M+) and base peak). This table (FIG. 13A) also contains similar GC/MS assay information for other higher diamondoids. While relative GC retention times are approximately constant, non-referenced GC retentions vary with time. It is recommended that GC/MS assay values be routinely updated especially when GC retention time drift is detected.
• Step 3 Feedstock Atmospheric Distillation
• Feedstock B was distilled into a number of fractions based on boiling points to separate the lower boiling point components (nondiamondoids and lower diamondoids) and for further concenfration and enrichment of particular higher diamondoids in various fractions.
• Feedstock B are shown in Table 1, below and are contrasted to simulated distillation yields. As seen from Table 1, the simulated distillation data is in agreement with the actual distillation data. The simulated distillation data were used to plan subsequent distillation processes.
• Table 4 illustrates the partial elemental composition of Feedstock B atmospheric distillation (650°F) residue including some of the identified impurities.
• Table 4 displays the weight percent nitrogen, sulfur, nickel and vanadium in Feedstock B atmospheric distillation residue. Subsequent steps remove these materials.
• a high-temperature reactor was used to pyrolyze and degrade a portion of the nondiamondoid components in various distillation fractions obtained in Step 4 (FIG. 12) thereby enricliing the diamondoids in the residue.
• the pyrolysis process was conducted at 450 °C for 19.5 hours.
• the gas chromatogram (FID) of fraction #6 (Table 3B) is shown in
• FIG. 18B is the chromatogram for the product of pyrolysis. A comparison of these chromatograms shows that pyrolysis has removed major nondiamondoid hydrocarbons and has significantly increased the higher diamondoid concenfration, especially the hexamantanes.
• Step 5 The pyrolysate produced in Step 5 was passed through a silica-gel gravity chromatography column (using cyclohexane elution solvent) to remove polar compounds and asphaltenes (Step 6, FIG. 12).
• a silver nitrate impregnated silica gel (10 weight percent AgNO 3 ) provides cleaner diamondoid-containing fractions by removing the free aromatic and polar components. While it is not necessary to use this chromatographic aromatic separation method, it facilitates subsequent steps.
• Step 7 Multi-column HPLC Isolation of Higher Diamondoids
• the first HPLC system consisted of two Whatman M20 10/50 ODS columns operated in series using acetone as mobile phase at 5.00 mL/min. A series of HPLC fractions were taken (see FIG. 19). Fractions 36 and 37 were combined and taken for further purification on a second HPLC system. This combined fraction (36 and 37) contained hexamantanes #7, #11 and #13. (FIG. 19, also see FIG. 13B).
• FIG. 20 shows elution times of the individual hexamantanes on the Hypercarb HPLC column (with acetone as a mobile phase).
• FIG. 51 A and 51B Other ODS HPLC fractions and Hypercarb HPLC cut points could be used to isolate the remaining hexamantanes. This isolation strategy is also applicable to the other higher diamondoids although elution solvent compositions can vary.
• the ODS and Hypercarb columns can also be used in reverse order for these isolations.
• i.e. fractionating hexamantane- containing ODS fractions using the Hypercarb or other suitable column and collecting at corresponding elution times can lead to the isolation of the remaining hexamantanes in high purity.
• Steps 1, 2, 3, 4, 5 and 6 of Example 1 were repeated (FIG. 12). The following variation of Step 7 was then carried out.
• a two-column preparative capillary gas chromatograph was used to isolate hexamantanes from the product of Example 1, Step 6.
• the cut times for the hexamantanes were set for the first preparative capillary the GC column, methyl silicone DB -1 equivalent, using the retention times and patterns from GC/MS assay (Example 1, Step 2).
• the results are shown in FIG. 42A, two cuts identified as "peaks cut and sent to column 2", were taken which contains two of the hexamantane components from Feedstock B.
• the preparative capillary gas chromatograph used was manufactured by Gerstel, Inc., Baltimore, Maryland, USA.
• the first column was used to concentrate the higher diamondoids, such as hexamantanes by taking cuts that were then sent to the second column (see FIG. 42B illustrated for hexamantane #2 and #8).
• the second column phenyl-methyl silicone, a DB-
• Steps 1, 2, 3,- and 4 (FIG. 12) of Example 1 were repeated using Feedstock A.
• Feedstock A is especially low in nondiamondoids in the atmospheric residue fraction recovered in Step 4.
• the pyrolysis Step (5) of Example 1 maybe omitted especially when the higher diamondoids being sought are tetramantanes, pentamantanes and cyclohexamantane.
• the fractions removed in Step 4 go directly to Steps 6 and 7 in Example 1 or directly to Step 7 in Example 2 (FIG. 12).
• This process variation can be applied to lower-boiling teframantane-containing fractions of Feedstock B as well.
• pyrolysis is highly desirable where significant nondiamondoid components are present.
• the first column was used to concentrate the target diamondoids (e.g., tetramantanes) by taking cuts that were then sent to the second column (phenyl-methyl silicone, a DB-17 equivalent) (see the bottom of FIG. 21).
• the second column further separated and purified the target diamondoids and then sent them into individual traps (traps 1-6).
• GC traps 2, 4 and 6 contained the selected tetramantanes (FIG. 21).
• the first column was used to concentrate the tetramantanes by taking cuts that were then sent to the second column (see FIG. 21).
• the second column phenyl-methyl silicone a DB-17 equivalent, further separated and purified the tetramantanes and then sent them into individual vials (traps 1-6). GC trap fractions 2, 4 and 6 were collected and further processed.
• FIG. 22A, B and C illustrate photomicrographs of tetramantane crystals isolated from Feedstock A in trap, #2, #4 and #6 corresponding to teframantane #1, #2, and #3 (respectively).
• EXAMPLE 5B Enrichment of Tetramantanes Using Pyrolysis.
• nondiamondoid components Prior to pyrolysis, nondiamondoid components are present (FIG. 23A) in a teframantane-containing fraction (distillation hold-up fraction similar in composition to Cut 1, FIG. 17). Pyrolysis degraded the nondiamondoid components to easily removable gas and coke-like solids. As shown in FIG. 23B, the nondiamondoid peaks are gone after pyrolysis. [000237] Pyrolysis was conducted by heating the tetramantane-rich distillation cut under vacuum in the reactor at 450 °C for 20.4 hours.
• EXAMPLE 5C Isolation of Tetramantanes Using a Single HPLC System.
• HPLC was also shown to provide sufficient enrichments of the tetramantanes to allow for their crystallization. Suitable columns for use are well known to those skilled in the art. In some cases, reverse-phase HPLC with acetone as mobile phase can be used to effect this purification.
• a preparative HPLC run of a Feedstock A, gas condensate, distillate fraction corresponding in cut point to Cut #1 (FIG. 17) was performed and the HPLC chromatogram recorded. Nine fractions where taken during the run.
• the HPLC columns used were two 25cm x 10mm ID.
• Vydac octadecyl silane ODS columns operated in series (Vydac columns are manufactured by The Separations Group, Inc., CA, USA).
• a 20 microliter sample of a solution of the teframantane-containing fraction at a concenfration of 55 mg/mL was injected into the columns.
• the columns were set-up using acetone at 2.00 ml/min as a mobile phase carrier.
• FIG. 24 compares the gas chromatogram of the starting material (FIG. 24 A) and HPLC fraction #6.
• HPLC Fraction #6 is significantly enriched in tetramantane
• FIG. 24B compared to the starting material (FIG. 24B compared to the starting material (FIG. 24A)).
• Tetramantane #2 in HPLC Fraction #6 is approaching a concentration sufficient to bring about its crystallization.
• tetramantanes can be isolated using HPLC methods.
• HPLC columns of different selectivities were used to isolate single tetramantane isomers.
• FIG. 25 shows a preparative separation of the tetramantanes using an octadecyl silane (ODS) HPLC column with acetone as a mobile phase.
• ODS octadecyl silane
• the distillation product used as starting material in Example 5B was the feedstock.
• preparative HPLC fractionation of the holdup fraction from Feedstock B atmospheric distillation taken at about 650°F were performed.
• the first column consisted of two Whatman M20 10/50 (x2) ODS columns operated in series using acetone at 5.00 ml/min as mobile phase (@590 psi),
• Tetramantane #3 elutes first, tetramantane #1 elutes second and tetramantane #2 elutes last on this Hypercarb HPLC system (FIG. 14). Tetramantane #2 was cut from this HPLC run (FIG. 26) and its purity illustrated in FIG.'s 28 A and B. Hypercarb HPLC runs on ODS HPLC cut led to isolation of all the tetramantanes (enantiomers are separatable by chiral HPLC methods).
• FIG. 27A shows the GC/MS total ion chromatogram (TIC) of an HPLC fraction containing tetramantane #1; and below it, FIG. 27B shows its mass spectrum.
• FIG. 29 A shows the GC/MS total ion chromatogram (TIC) of an HPLC fraction containing isolated tetramantane #3; and below FIG. 29B shows the mass spectrum.
• Alkyltetramantanes can be purified using methodologies described for nonalkylated tetramantanes given in Examples 5A to 5D.
• FIG. 30 shows an isolated monomethylated tetramantane with molecular weight of 306 yielding a mass spectrometric molecular ion of m/z 306, and shows a mass spectrometric loss of the methyl group giving the m/z 291 mass spectrometric fragment ion (indicative of a tetramantane moiety).
• This alkylated compound was isolated by Hypercarb HPLC and shows a retention time of 11.46 minutes in our GC/MS system (FIG. 30). It may be necessary to use additional HPLC separations or preparative GC (as is Examples 3 and 4) to isolate some alkyltetramantanes.
• Step 5 5.2 g. of Feedstock B 650°F + bottoms distillation cut 5 (Table 3, FIG. 18) was pyrolyzed under vacuum at 450°C for 16.7 hours. This product was then treated in accord with Example 1 Step 6.
• the two-column preparative capillary gas chromatograph was then used to isolate pentamantanes from the product of Step 6 above.
• An exemplary result is shown for pentamantane #1 in FIG. 31.
• the pentamantane #1 -containing GC peak on the first column is identified as "peak cut and sent to column 2" in FIG. 31 A.
• the first column was used to concentrate the pentamantane by taking a cut that was then sent to the second column.
• the second column phenyl-methyl silicone, a DB-17 equivalent, further separated the pentamantane #1 from other materials.
• the material in the peak of interest identified as "peak sent to trap” was sent to GC trap fraction 6 where crystals of pentamantane #1 accumulated (see FIG. 31B).
• GCMS analysis of trap #6 material (FIG. 32) showed it to be pentamantane #1 (in the pentamantane reference GCMS retention time system set-up for this preparative GC procedure, the first eluting pentamantane (#1) showed a retention time of 16.233 min.
• FIG's. 32A and B show the high purity of pentamantane #1 removed from GC frap 6. This procedure could be repeated to isolate the four other pentamantanes and three enantiomeric pairs which could be separated using chiral HPLC or other resolution techniques
• FIG. 33A is a photomicrograph of two pentamantanes that co-crystallized in a preparative GC trap.
• non-enantiomeric pentamantane materials could be sent for structural determination using X-ray diffraction. Enantiomeric pentamantanes can undergo further separations to resolve their two components.
• Pentamantane #l-containing ODS HPLC fractions indicated in FIG. 34 were further purified using Hypercarb HPLC (FIG. 35) to isolate pentamantane #1.
• FIG. 14 shows how ODS HPLC and Hypercarb HPLC can be used together to isolate the remaining pentamantanes. The ODS and Hypercarb columns can also be used in reverse order for this isolation.
• FIG. 36 shows the GC/MS total ion chromatogram (TIC) of the isolated pentamantane #1. The lower half of FIG. 36 illusfrates the mass spectrum of the pentamantane #1 GC/MS peak. As indicated in FIG's. 14 and 34, the various remaining
• ODS HPLC fractions contain other pentamantanes.
• fractionating pentamantane containing ODS fractions using the Hypercarb (as indicated in FIG. 14) or another suitable column, and collecting at corresponding elution times leads to the isolation of the remaining pentamantanes in high purity as shown in FIG's 37-41.
• FIG. 37 illustrates GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #2 isolated using two different HPLC columns
• FIG. 38 illustrates GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #3 isolated using two different HPLC columns
• FIG. 39 illusfrates GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #4 isolated using two different HPLC columns
• FIG. 40 illustrates GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #5 isolated using two different HPLC columns
• Substituted pentamantanes are present in Feedstocks A and B. Substituted pentamantanes can be enriched from these feedstocks and purified using methodologies described for nonalkylated pentamantanes in Examples 1-4.
• the monomethylated pentamantane enriched in this instance has a molecular weight of 358 (yielding a mass spectrometric molecular ion of m/z 358, and shows a mass spectrometric loss of the methyl group giving the m/z 343 mass spectrometric fragment ion indicative of a pentamantane moiety).
• This alkylated compound was enriched in ODS HPLC fraction #31 and could be further purified to form a crystal by an additional HPLC separation, or alternatively by a preparative GC procedure (as is Example 3).
• Example 2 The purpose of this example is to demonstrate procedures which can be used for the enrichment and isolation of the thirty-nine hexamantane components.
• the process of Example 1 was repeated with the following changes, hi Step 5, 34.4 g. of Feedstock B 650°F bottoms distillation cut #6 (Table 3, FIG. 18) was pyrolyzed under vacuum at 450°C for 17.3 hr.
• the eluent from the column chromatography (Step 6) was analyzed by GC/MS to determine the GC retention times of hexamantanes. individual hexamantane components with molecular weight 396 were assigned a number according to their elution order on this GC/MS assay.
• FIG. 13 A lists another GC/MS assay result for the hexamantane components
• a two-column preparative capillary gas chromatograph was used to isolate hexamantanes from the distillate fractions cleaned-up by column chromatography.
• the cut times for the hexamantanes were set for the first preparative capillary GC column, methyl silicone DB -1 equivalent, using the retention times and patterns from GC/MS assay.
• the results are shown in FIG. 42 A, identified as "peak cut and sent to column 2" which contains two of the hexamantane fractions.
• the first column was used to concentrate the hexamantanes by taking cuts that were then sent to the second column (see FIG. 42 illusfrated for hexamantane #2 and #8).
• the second column phenyl-methyl silicone a DB-17 equivalent, further separated and purified the hexamantanes and then was used to isolate peaks of interest and retain them into individual traps (traps 1-6).
• GC trap fraction 1 was collected and further processed for the separation of hexamantane #2.
• GC trap fraction 3 was collected and further processed for the separation of hexamantane #8. Subsequent GC/MS analysis of trap #1 material (FIG.
• FIG. 46 is a photomicrograph of hexamantane #8 that crystallized in preparative GC trap 3. Crystals of hexamantane #8 had never existed before this isolation.
• non-enantiomeric hexamantane components could be sent for structural determination using X-ray diffraction. Enantiomeric hexamantanes must undergo further separations to resolve the two components.
• EXAMPLE 7B Isolation of Hexamantanes Using a Single HPLC System.
• HPLC columns used were two 50cm x 20mm ID. Whatman octadecyl silane (ODS) columns operated in series (Whatman columns are manufactured by Whatman hie, USA).
• ODS Whatman octadecyl silane
• the columns were setup using acetone at 5.00 ml/min as the mobile phase.
• Some of the HPLC fractions reached the purity necessary for individual hexamantanes to crystallize as shown for Hexamantane # 8 in ODS HPLC fraction # 39 (FIG. 47), Hexamantane # 10 in ODS HPLC fraction # 48 (FIG.
• Feedstock B distillate cut 6 pyrolysis product saturated hydrocarbon fraction was performed and the HPLC chromatogram recorded using a differential refractometer. Fractions (e.g., FIG. 50) where taken during the run and showed that most hexamantanes display different elution times (verified by GC/MS analysis) from one another on the Hypercarb HPLC system (FIG. 20).
• EXAMPLE 7C Isolation of Hexamantanes Using Multiple HPLC Columns of
• FIG. 52 shows the GC/MS total ion chromatogram (TIC) of the hexamantane #7 containing Hypercarb HPLC fraction. The lower half of FIG. 52 illustrates the mass spectrum of the GC/MS peak, demonstrating the high purity of the isolated hexamantane #7.
• FIG.'s 53 and 54 present reconstructed ion chromatograms for m/z 382 showing hexamantanes running at 18.30 min. and 18.07 min., respectively.
• FIG.'s 53 and 54 also show the corresponding mass spectra for these 18.30 min. and 18.07 min. peaks, demonstrating the presence of hexamantanes with a 382 molecular weight in the saturated hydrocarbon fraction from the product of pyrolytic processing of Feedstock B distillation fraction #6.
• the 382 molecular weight hexamantanes show internal bond strain, lower stability, and correspondingly lower concentrations than the 396 molecular weight hexamantanes, making the 382 molecular weight hexamantanes the less preferred hexamantanes.
• Substituted hexamantanes including alkylhexamantanes also are present in Feedstock A and B. These natural substituted hexamantanes have uses similar to the unsubstituted hexamantanes, can act as useful intermediates in various hexamantane applications (e.g., polymer production) and can be de-alkylated to yield the corresponding underivatized hexamantane. Accordingly, methods for the isolation of individual substituted hexamantane were devised and exemplified by the isolation of alkyl substituted components.
• Substituted hexamantanes can be isolated in high purity using a single HPLC separation of appropriate distillation cuts as exemplified by FIG. 55.
• FIG. 55 shows that fraction #55 from an ODS HPLC separation of the saturated hydrocarbon fraction from Feedstock B, distillation fraction 6 pyrolysis contains a methylated hexamantane in high purity.
• Monomethylated hexamantanes have a molecular weight of 410 (yielding a mass spectrometric molecular ion of m/z 410, and show a mass spectrometric loss of the methyl group giving the m/z 395 fragment ion (FIG. 55B)).
• Isolation of substituted hexamantane components by HPLC may require multiple columns with different selectivities.
• the ODS and Hypercarb HPLC columns were run in succession to isolate the methylcyclohexamantane components (methyl-substituted mol. weight 342 hexamantane) from distillation cut 6-pyrolysis product saturated hydrocarbon fraction.
• fractions #23-26 were combined and taken for further purification on a second HPLC system.
• This combined fraction (FIG. 56) contained a mixture of hexamantane (mol.
• FIG. 59 illustrates a methylcyclohexamantane crystal precipitated from Hypercarb HPLC fractions #19-21
• FIG. 60 illustrates a methylcyclohexamantane crystal precipitated from Hypercarb HPLC fractions #23.
• Enantiomeric pairs must undergo further separations to resolve the two components. After obtaining crystals of suitable size, non-enantiomeric alkylhexamantanes can be sent for structural determination by x-ray crystallography.
• a two-column preparative capillary gas chromatograph was then used to isolate heptamantanes from the distillate fractions cleaned-up by column chromatography.
• the cut times for the heptamantanes were set for the first preparative capillary GC column, methyl silicone DB -1 equivalent, using the retention times and patterns from GC/MS assay (from Step 2 above, FIG. 12).
• An exemplary result is shown in the top of FIG. 61, identified as "peak cut and sent to column 2" which contains two of the heptamantanes from Feedstock B.
• the first column was used to concentrate the heptamantanes by taking cuts that were then sent to the second column (see FIG. 61 illustrated for heptamantanes #1 and #2).
• the second column phenyl-methyl silicone a DB-17 equivalent, further separated and purified the heptamantane components and then was used to isolate peaks of interest and retain them in individual vials (traps 1-6).
• GC trap fraction 2 was collected and further processed for the separation of heptamantane #1.
• GC trap fraction 4 was collected and further processed for the separation of heptamantane #2. Subsequent GC/MS analysis of trap #2 material (FIG.
• FIG. 65 is a photomicrograph of heptamantane component #2 that crystallized in preparative GC trap 4. Crystals of heptamantane component #2 had never existed before this isolation.
• heptamantane materials could be sent for structural determination using X-ray diffraction. Enantiomeric heptamantanes can undergo further separations to resolve their two components.
• HPLC was also shown to provide sufficient enrichments of some heptamantanes to allow for their crystallization.
• the higher diamondoids in various HPLC fractions could be separated using further chromatographic techniques including preparative gas chromatography and additional HPLC runs using columns of different selectivity as outlined below. Additionally other techniques known in the crystallization art could be utilized including but not limited to fractional sublimation, progressive recrystalization or zone refining could be used to purify the heptamantanes.
• Substituted heptamantanes including alkylheptamantanes also are present in Feedstock A and B.
• Alkylheptamantanes can be purified by removal of nondiamondoid impurities from feedstocks using pyrolysis as shown above. Certain alkylheptamantanes survive pyrolysis processing, as do the heptamantane components previously identified.
• Substituted heptamantanes including alkylheptamantanes can be isolated in high purity using a single HPLC separation as exemplified by FIG. 74.
• Monomethylated heptamantanes have a molecular weight of 408 (yielding a mass spectrometric molecular ion of m/z 408, and show a mass spectrometric loss of the methyl group giving the m/z 393 mass spectrometric fragment ion indicative of a heptamantane moiety (FIG. 74B).
• FIG. 75 illustrates a GC/MS total ion chromatogram and mass spectra of an HPLC fraction in which octamantane #1 has been purified to the point where it formed crystals (see FIG. 76).
• HPLC Fraction 63 yielded octamantane #3 and #5 together (FIG. 77), which co-crystallized from the fraction (FIG. 78).
• Alkyloctamantanes can be purified using methodologies described for nonalkylated octamantanes given in Examples 1 and 3.
• FIG. 81(A B) shows that ODS HPLC fraction 94 contains a methylated octamantane in high purity.
• Monomethylated octamantanes have a molecular weight of 460 (yielding a mass spectrometric molecular ion of m/z 460, and show a mass spectrometric loss of the methyl group giving the m/z 445 mass spectrometric fragment ion indicative of an octamantane moiety (FIG. 8 IB).
• an additional HPLC separation of that fraction or preparative GC procedure (as in Example 3) can yield high purity alkyloctamantanes.
• HPLC columns For isolation of nonamantane components in high purity, multiple HPLC columns can be employed. To illustrate this methodology, HPLC columns of different selectivities ODS and Hypercarb (as described in previous examples) were used in succession to isolate a single nonamantane. From the ODS HPLC run, the nonamantane containing fractions 84-88 (FIG. 13B) were combined for further purification on a Hypercarb HPLC system.
• FIG. 83 shows the GC/MS total ion chromatogram (TIC) of the concentrated nonamantane containing Hypercarb HPLC fraction.
• TIC total ion chromatogram
• the lower half of FIG. 83 illustrates the mass spectrum of the GC/MS peak.
• Nonamantane was isolated by a third HPLC run using the same Hypercarb stationary phase column but with a solvent consisting of methylene chloride/acetone (70:30 volume percent operating at 1.00 ml/min). The resulting isolated nonamantane crystal and corresponding mass spectrum are shown in FIG. 84.
• Substituted nonamantanes also are present in Feedstock A and B.
• Alkylnonamantanes can be purified using methodologies described for non-alkylated nonamantanes.
• FIG. 85(A/B) shows methylated nonamantane in a pyrolysis product of distillate fraction #7.
• One type of monomethylated nonamantane has a molecular weight of
• HPLC columns For isolation of decamantane components in high purity, multiple HPLC columns can be employed. To illustrate this methodology, HPLC columns of different selectivities were used in succession to isolate a single decamantane. The first HPLC system consisted of the same ODS columns described previously. From this HPLC run, the decamantane containing fractions 74-83 were combined for further purification on a second HPLC system. Five such runs were completed and all decamantane containing fractions from the runs were combined. This combined fraction contained a molecular weight 456 decamantane and various impurities.
• FIG. 87 shows the GC/MS total ion chromatogram (TIC) of the concentrated decamantane-containing Hypercarb HPLC fraction eluting at 18.55 minutes.
• the lower half of FIG. 87 illusfrates the mass spectrum of the GC/MS peak with a prominent peak at m z
• Substituted decamantanes also are present in Feedstock A and B.
• Alkyldecamantanes can be purified using methodologies described for non-alkylated decamantanes.
• FIG. 90 shows that saturated fraction of the pyrolysis product of distillate fraction #7 contains methylated decamantanes.
• One type of monomethylated decamantane has a molecular weight of 470 (yielding a mass specfrometric molecular ion of m/z 470).
• an additional HPLC separation of that fraction or an alternative preparative GC procedure can yield high purity alkyldecamantanes.
• EXAMPLE 12 Isolation of Undecamantane Components
• the concentrated undecamantane from ODS HPLC fraction 100+ (FIG. 13B) is shown in FIG. 92.
• This fraction could be purified on a Hypercarb HPLC using a system (similar to that explained in Example 11) to isolate undecamantane.
• This method could be repeated to isolate the undecamantanes with molecular weights of 656 and/or 602, as well as molecular weights 642,628, 588, 548 or 534 which respectively are anticipated to be in lower abundance in our feedstocks.

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