CN1256310C - Compositions including higher diamondoids and methods for their isolation - Google Patents

Abstract

Disclosed are isolated and enriched forms of higher diamondoids from tetramantane to undecamantane. Also disclosed are methods for obtaining these higher diamondoids.

Description

Compositions including higher diamondoids and methods for their isolation

Background of the invention

Field of the invention

The present invention relates to isolated or enriched higher diamondoid components and to compositions comprising one or more higher diamondoid components. The present invention also relates to a novel process for the separation and isolation of higher diamondoid components into recoverable fractions from feedstocks containing one or more higher diamondoid components.

references

The following publications and patents are referenced in this application as superscript numbers:

¹ Fort, Jr. et al., Adamantane: Consequences of the Diamondoid Structure, Chem. Rev.,: 277-300 (1964).

² Sandia National Laboratories (2000), World's First Diamond Micromachines Created at Sandia, Press Release, (2/22/2000) www.Sandia.gov.

³ Lin et al., Natural Occurrence of Tetramantane (C ₂₂ H ₂₈ ), Pentamantane (C ₂₆ H ₃₂ ) and Hexamantane (C ₃₀ H ₃₆ ) in a Deep Petroleum Reservoir, Fuel, (10): 1512-1521 (1995).

⁴ Chen et al., Isolation of High Purity Diamondoid Fractions and Components, US Patent No. 5,414,189, issued May 9, 1995.

⁵ Alexander et al., Removal of Diamondoid Compounds from Hydrocarbonaceous Fractions, US Patent No. 4,952,747, issued August 28, 1990.

⁶ Alexander et al., Purification of Hydrocarbonaceous Fractions, US Patent No. 4,952,748, issued August 28, 1990.

⁷ Alexander et al., Removal of Diamondoid Compounds from Hydrocarbonaceous Fractions, US Patent No. 4,952,749, issued August 28, 1990.

⁸ Alexander et al., Purification of Hydrocarbonaceous Fractions, US Patent No. 4,982,049, issued January 1, 1991.

⁹ Swanson, Method for Diamondoid Extraction Using a Solvent System, US Patent No. 5,461,184, issued October 24, 1995.

¹⁰ Partridge et al., Shape-Selective Process for Concentrating Diamondoid-Containing Hydrocarbon Solvents, US Patent No. 5,019,665, issued May 28, 1991.

¹¹ Dahl et al., Diamondoid Hydrocarbohs as Indicators of Natural Oil Cracking, Nature, 54-57 (1999).

¹² McKervey, Synthetic Approaches to Large Diamondoid Hydrocarbons, Tetrahedron, 971-992 (1980).

¹³ Wu et al., High Viscosity Index Lubricant Fluid, US Patent No. 5,306,851, issued April 26, 1994.

¹⁴ Chung et al., Recent Development in High-Energy Density Liquid Fuels, Energy and Fuels, 641-649 (1999).

¹⁵ Balaban et al., Systematic Classification and Nomenclature of Diamond Hydrocarbons-1, Tetrahedron, 34, 3599-3609.

All of the above publications and patents are herein incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference in its entirety.

Diamondoids are hydrocarbon molecules with a surprisingly rigid structure containing a framework of carbon atoms that can be superimposed on a diamond ^lattice1 (see Figure 1). Adamantane, a ten-carbon molecule, is the smallest member of the diamondoid series and consists of a caged diamond crystal subunit. Adamantane is commercially available and widely used as a chemical intermediate. It can be synthesized and recovered from petroleum. Diamantane contains two face-fused diamond subunits and triamantane contains three. These three feedstocks have been synthesized and isolated from petroleum and have been extensively studied. Adamantane, diamantane and triamantane are classified as lower diamondoids. Tetramantane, pentamantane, etc. have different properties from lower diamondoids (including multiple isomers, chirality and, above tetramantane, multiple molecular weight forms) and are classified as higher diamondoids. Although only one of the higher diamondoids has been synthesized, concepts regarding their structure and hypothetical properties have been elucidated.

Although there are no isomers shown for adamantane, diamantane, and triamantane, it is understood that there should be four different isomers of tetraamantane; there are diamonds that can be superimposed on the diamond lattice in different ways - Four different shapes of cage subunits. Two of these isomers are enantiomers (mirror images of each other). Since the four tetramantanes each have ten faces, the next diamond-cage unit can be fused to each face, so there are more pentamantanes than tetramantanes. The number of possible isomers will increase rapidly with each higher member of the diamondoid series. Also, because diamondoid crystal units can share more than one face within some higher diamondoids, the ratio of hydrogen to carbon, i.e., the degree of condensation, also exhibits increased variation, resulting in each successive higher diamondoid The greater diversification of the molecular weight of the family (Figure 1). Figure 2 is a table showing the different series of molecular weights calculated for higher diamondoids ranging from tetramantane to undecamantane.

Lower diamondoids are present in almost every kind of petroleum (oil and gas condensates) and oil source-rock extracts. ¹¹ Natural concentrations of diamondoids in petroleum can vary by orders of magnitude. For example, the concentration of methyldiamantane in less mature crude oils from the Central Rift Valley in California is on the order of parts per million (ppm). Low maturity oils in the Jurassic Smackover formations originating from the Gulf Coast of the United States have methyldiamantane concentrations of 20-30 ppm. Because diamondoids exhibit much greater stability than other petroleum hydrocarbons, deeply buried petroleum, which undergoes significant cracking due to high temperatures, can have methyldiamantane concentrations of several thousand ppm. It is not understood how advanced diamondoids can form in natural systems, but it involves an evolutionary process that takes millions of years.

Higher diamondoids, including tetramantane, pentamantane, etc., have received less attention. In fact, these compounds hypothetically had only one such compound that had been synthesized and attempts to Several other isomers were definitively verified (however not isolated). More specifically, McKervey et al. reported the synthesis of trans-tetramantane in relatively low yields by using a laborious, multi-step process. ¹² Higher diamondoids cannot be synthesized by the carbocation isomerization method used for lower diamondoids. Lin et al. only confirmed the presence of tetramantane, pentamantane and hexamantane in deep oil formations from mass spectrometry, but did not make any attempt to isolate these substances. ³ The possible presence of tetramantane and pentamantane in tank stock recovered after distillation of diamondoid-containing feedstock has been discussed by Chen et al. ⁴ Again, they made no attempt to isolate these substances from the tank stock.

As additional background, it may be noted that the present inventors have separately isolated the higher diamondoid cyclohexamantane, the most condensed member of the hexamantane series, and made this invention the subject of its own patent application.

In summary, higher diamondoids have not been previously identified or isolated or otherwise provided the following exceptions: iso-tetramantane - synthesized ¹² and unsubstituted cyclohexamantane - discovered solely by the present inventors.

Summary of the invention

The present invention provides higher diamondoids as enriched or isolated compounds. Also provided are individual higher diamondoid isomers (for the first time the higher diamondoid component is referred to as an enriched or isolated compound). In addition, the present invention provides methods by which enriched and isolated higher diamondoids and higher diamondoid components can be obtained.

According to the present invention, we have isolated various previously unavailable higher diamondoids as crystals, including tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, And even ten adamantanes. The isolation of higher molecular weight higher diamondoids was particularly unexpected in view of our finding that the relative abundance of each diamondoid family (tetra versus penta(adamantane), etc.) For each crystal subunit in , it will decrease by about 10 times. This means that we are isolating decamantane, for example, about 10 ^-6 times as much as any of the tetramantanes in common starting materials, including those synthesized in the prior art.

Brief description of the drawings

Figure 1 illustrates the cage structures of diamondoids and their relationship to diamond. Specifically illustrated is the interrelationship of the diamondoid structure with the subunits of the diamond lattice.

Figure 2 is a table depicting the different molecular weights exhibited by each higher diamondoid series.

Figure 3 illustrates the structure of tetramantane provided by the present invention.

Figure 4 illustrates that four tetraadamantanes have a carbon framework associated with the diamond-type lattice and observed as their 100 lattice plane (Fig. 4A), 110 lattice plane (Fig. 4B) and 111 diamond-type lattice plane (Fig. 4C).

Figure 5 illustrates the structures of pentamantanes provided by the present invention.

Figures 6A, 6B, 6C and 6D illustrate the structures of the hexamantanes provided by the present invention.

Figures 7A and 7C illustrate the structures of the heptamantanes provided by the present invention. Only one of each enantiomer is shown.

Figure 8 illustrates the structures of octamantanes provided by the present invention. Only examples of the 500, 486, 472 and 432 molecular weight forms are shown.

Figure 9 illustrates the structures of nonamantanes provided by the present invention. Only examples for each molecular weight family are shown.

Figure 10 illustrates the structures of decamantanes provided by the present invention. Only examples for each molecular weight family are shown.

Figure 11 illustrates the structures of the undecamantanes provided by the present invention. Only examples for each molecular weight family are shown.

Figure 12 presents a flow chart representing the various steps used in the isolation of the higher diamondoid-containing fraction and the various higher diamondoid components. It should be noted that in some cases the steps could be used in a different order and possibly skipped, as discussed in the Examples.

Figures 13A and 13B are compilations of the GC/MS and HPLC properties of various higher diamondoids included in this application.

Figure 14 shows a two-HPLC column strategy for the isolation of individual tetramantane and pentamantane.

Figure 15 illustrates the size and shape of selected higher diamondoids relative to C60 (Buckminster-fullerene) and representative carbon nanotubes used in the development of molecular electronic devices. The carbon framework structures of selected diamondoids can be seen in FIGS. 5 , 6 , 8 , 9 and 10 .

Figure 16 shows that the gas chromatogram of the gas condensate feedstock - one of the starting feedstocks used in the examples (Feedstock A) - shows the lowest concentration of advanced diamond (not detected on this scale).

Figure 17 illustrates the high temperature simulated distillation profile for feedstock B, using atmospheric distillation 650°F+ bottoms as the feedstock. The figure also illustrates the target cut point (1-10) used by us for the isolation of higher diamondoids.

Figures 18A and 18B illustrate distillate fraction #6 of Feedstock B 650°F + distillation bottoms (Table 3B, Figure 18), and the gas chromatogram (FID) of the product obtained during the thermal decomposition process. These figures show that the non-diamondoid components have been destroyed by the pyrolysis process, while the higher diamondoids, especially hexamantanes, have been concentrated and are available for isolation operations.

Figures 19 and 20 are the elution sequences of a number of each higher diamondoid (hexamantane) on two different HPLC chromatographic columns: ODS and Hypercarb discussed in Examples 1 and 7.

Figures 21A and 21B illustrate preparative capillary gas chromatography data for the isolation of tetramantanes performed in Examples 3 and 5. Figure 21A shows the cuts taken for feedstock A for distillate fraction #33. Numbers in bold refer to the peaks of tetramantane. Figure 21B shows the peaks isolated and sent to the collector. The circled numbered peaks (2, 4 and 6) are tetramantanes. It should be noted that the two enantiomers of the optically active tetramantane are contained in one of these peaks.

Figures 22A, 22B and 22C illustrate photomicrographs of tetramantane crystals isolated from starting material A by preparative gas chromatography (Figure 21). Figure 22A is isolated from pooled fraction #2, Figure 22B is isolated from pooled fraction #4, and Figure 22C is isolated from pooled fraction #6. Since the two enantiomeric tetramantanes have the same GC retention time in Figure 21, one of these crystals contains both enantiomers.

Fig. 23A illustrates the gas chromatogram of the atmospheric distillation retentate fraction of feedstock B exemplified in the Examples, which was used as the feedstock in the thermal decomposition process. The retentate is the material recovered from the distillation column after distillation of Feed B at about 650°F. Tetramantanes #1 to #3 are shown.

Figure 23B illustrates a gas chromatogram of the pyrolysis product from the starting material in Figure 23A, ie, the retentate fraction of the atmospheric distillation 650°F+ bottoms of Feedstock B, showing degradation of non-diamondoid components.

Figures 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 the tetramantane component.

Figure 25 illustrates the preparative ODS HPLC isolation of the hold-up fraction of the atmospheric distillation 650°F+ bottoms of feedstock B, showing the fractions selected at each retention time and the elution order of the tetramantane component and the subsequent isolation steps. Location time of fraction #12 used in . Figure 23 above shows the gas chromatogram for this feedstock.

Figure 26 illustrates the HPLC chromatogram of Fraction 12 (Figure 25) on a Hypercarb stationary phase with an acetone mobile phase, resulting in the isolation of tetramantane #2.

Figures 27A and 27B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of Tetramantane #1 isolated by using two different HPLC columns.

Figures 28A and 28B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of Tetramantane #2 isolated by using two different HPLC columns.

Figures 29A and 29B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of Tetramantane #3 isolated by using two different HPLC columns.

Figures 30A and 30B show the GC/MS total ion chromatogram (TIC) and mass spectrum of methyltetramantane isolated by using Hypercarb HPLC.

Figures 31A and 31B illustrate preparative capillary gas chromatography data for the isolation of pentamantane. Figure 31A shows the first column cut containing one of the pentamantanes from heat-treated feedstock B. The material in this cut is then separated in a second column. Figure 3 IB shows the second column peak sent to the trap. Pentamantane #1, the first pentamantane to elute in the GC/MS analysis, was isolated in collector 6.

Figures 32A and 32B show the GC/MS total ion chromatogram and mass spectrum of pentamantane #1 isolated by preparative capillary gas chromatography.

Figure 33A is a photomicrograph of pentamantane #1 crystals isolated from starting material B by preparative gas chromatography (Figures 31 and 32). Figure 33B illustrates a pentamantane co-crystal.

Figure 34 illustrates the preparative HPLC refractive index trace (with negative polarity) of the FeedstockB distillate cut pyrolysis product saturated hydrocarbon fraction, showing the peak value obtained using an octadecylsilane column. and acetone mobile phase obtained HPLC fractions. Pentamantanes are numbered according to their elution order on GC/MS analysis.

Figure 35 illustrates the chromatogram of ODSHPLC fraction 11 (Figure 34) run on a Hypercarb stationary phase with an acetone mobile phase, resulting in the isolation of pentamantane #1.

Figures 36A and 36B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #1 isolated by using two different HPLC columns.

Figures 37A and 37B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #2 isolated by using two different HPLC columns.

Figures 38A and 38B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #3 isolated by using two different HPLC columns.

Figures 39A and 39B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #4 isolated by using two different HPLC columns.

Figures 40A and 40B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #5 isolated by using two different HPLC columns.

Figures 41A and 41B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #6 isolated by using two different HPLC columns.

Figures 42A and 42B illustrate preparative capillary gas chromatography data for the isolation of hexamantane. Figure 42A shows the first column fraction containing two of the hexamantanes from feedstock B. Figure 42B shows the second column peak that was isolated and sent to the collector. From this procedure, pure hexamantanes were isolated (Figures 43 and 44), hexamantane #2, the second hexamantane that needed to elute in our GC/MS analysis, and hexamantane #8 was the desired The eighth type of elution.

Figures 43A and 43B illustrate the GC/MS total ion chromatogram and mass spectrum of hexamantane #2 isolated by preparative capillary gas chromatography.

Figures 44A and 44B illustrate the GC/MS total ion chromatogram and mass spectrum of highly concentrated hexamantane #8 by preparative capillary gas chromatography. A small amount of methylheptamantane (408 molecular weight) was present in this sample.

Figure 45 illustrates a photomicrograph of hexamantane #2 crystals isolated from feedstock B by preparative gas chromatography (Figures 42 and 44).

Figure 46 illustrates a photomicrograph of hexamantane #8 crystals isolated from starting material B by preparative gas chromatography (Figures 145 and 147).

Figures 47A and 47B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #8 in ODS HPLC fraction #39.

Figures 48A and 48B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #10 in ODS HPLC fraction #48.

Figures 49A and 49B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #6 in ODS HPLC fraction #63.

Figures 50A and 50B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #2 in Hypercarb HPLC fraction #53.

Figures 51A and 51B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #13 isolated by using two different HPLC columns.

Figures 52A and 52B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of hexamantane #7 isolated by using two different HPLC columns.

Figures 53A and 53B illustrate the GC/MS reconstructed ion chromatograms of concentrated "irregular" hexamantane (molecular weight 382) in the saturated hydrocarbon fraction of the product of the thermal decomposition process of feedstock B distillation fraction #6 m /z 382 and mass spectrometry.

Figures 54A and 54B illustrate the GC/MS reconstructed ion chromatogram m/z 382 and mass spectrum of irregular hexamantane (molecular weight 382) in ODS HPLC fraction #36.

Figures 55A and 55B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of methylhexamantane (MW 410) isolated in ODS HPLC fraction #55.

Figure 56 illustrates the GC/MS total ion chromatogram (TIC) of ODS HPLC pooled fractions #23-26 containing cyclohexamantane and methylcyclohexamantane.

Figures 57A and 57B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of methylcyclohexamantane #1 (molecular weight 356) isolated by using multi-column stationary phase HPLC (ODS followed by Hypercarb).

Figures 58A and 58B illustrate the GC/MS total ion chromatogram (TIC) of methylcyclohexamantane #2 (MW 356) isolated in high purity by using multi-column stationary phase HPLC (ODS followed by Hypercarb) and mass spectrometry.

Figures 59 and 60 show micrographs of crystals of methylcyclohexamantane #1 and methylcyclohexamantane #2 isolated by using two different HPLC columns.

Figures 61A and 61B illustrate preparative capillary gas chromatography data for the isolation of heptamantane. Figure 61A shows the first column fraction containing two of the heptamantanes from feedstock B. Figure 61B shows the second column peak that was isolated and sent to the collector. From this procedure it was possible to isolate the pure heptamantane component (Figures 8 and 9), heptamantane #1, the first heptamantane to elute in our GC/MS analyses, and heptamantane #2 is the second one that needs to be eluted.

Figures 62A and 62B illustrate the GC/MS total ion chromatogram and mass spectrum of heptamantane #1 isolated by preparative capillary gas chromatography.

Figures 63A and 63B illustrate the GC/MS total ion chromatogram and mass spectrum of heptamantane #2 highly concentrated by preparative capillary gas chromatography.

Figure 64 illustrates a photomicrograph of heptamantane #1 crystals isolated from starting material B by preparative gas chromatography (Figures 61 and 62).

Figure 65 illustrates a photomicrograph of heptamantane #2 crystals isolated from starting material B by preparative gas chromatography (Figures 61 and 63).

Figures 66A and 66B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane fraction #1 in ODS HPLC fraction #45.

Figures 67A and 67B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane fraction #2 in ODS HPLC fraction #41.

Figures 68A and 68B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane component #9 in ODS HPLC fraction #61.

Figures 69A and 69B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane fraction #10 in ODS HPLC fraction #87.

Figures 70A and 70B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane #1 in Hypercarb HPLC fraction #55.

Figures 71A and 71B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of heptamantane #2 isolated by using two different HPLC columns. Heptamantane #2 was isolated from ODS HPLC fraction #41 (Figure 67) by using a Hypercarb HPLC system.

Figure 72 illustrates the GC/MS reconstructed ion chromatogram m/z 420 showing a partially condensed heptamantane component (molecular weight 420) in ODS HPLC fraction #61.

FIG. 73 illustrates the mass spectrum of heptamantane of molecular weight 420 in FIG. 72 .

Figures 74A and 74B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of the methylheptamantane component (molecular weight 408) isolated in ODS HPLC fraction #51.

Figures 75A and 75B illustrate the GC/MS total ion chromatogram and mass spectrum of octamantane #1 highly concentrated by high performance liquid chromatography.

Figure 76 illustrates a photomicrograph of octamantane #1 crystals isolated from starting material B by high performance liquid chromatography.

Figures 77A and 77B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of co-crystal octamantane #3 and octamantane #5 (Figure 78) grown from ODS HPLC fraction #63.

Figures 78A and 78B illustrate photomicrographs of co-crystal octamantane #3 and #5, crystal B dissolved in cyclohexane and analyzed by GC/MS (Figure 77).

Figures 79A and 79B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of ODSHPLC fraction #80 containing octamantane #1 and octamantane #10.

Figures 80A and 80B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of ODS HPLC fraction #92 containing octamantane (MW 500).

Figures 81A and 81B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of methyloctamantane (MW 460) in ODS HPLC fraction #94.

Figures 82A and 82B illustrate the GC/MS total ion chromatogram and mass spectrum of nonamantane concentrated by high performance liquid chromatography.

Figures 83A and 83B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of nonamantane concentrated by using two different HPLC columns.

Figures 84A and 84B illustrate photomicrographs of nonamantane crystals and mass spectra of dissolved crystals.

Figures 85A and 85B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of methylnonamantane (molecular weight 512).

Figures 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.

Figures 87A and 87B illustrate the GC/MS total ion chromatogram (TIC) and mass spectrum of [1231241(2)3], molecular weight 456, decamantane isolated by using two different HPLC columns.

Figures 88A and 88B illustrate micrographs of [1231241(2)3], molecular weight 456, decamantane crystals, and mass spectra of dissolved crystals.

Figures 89A and 89B illustrate the GC/MS Selected Ion Chromatogram (TIC) and mass spectrum of decamantane (MW 496).

Figures 90A and 90B illustrate the GC/MS total ion chromatograms (TICs) of two methyldecadamantanes (MW 470), and the mass spectrum of one eluting at 18.84 min. in GC/MS analysis.

91A and 91B illustrate the GC/MS selected ion chromatogram (m/z 508) and mass spectrum of the pyrolysis product of enriched undecadamantane of Feedstock B atmospheric distillation fraction #7 (Table 3).

Figures 92A, 92B and 92C illustrate the GC/MS Selected Ion Chromatogram (m/z 508) and mass spectrum of the undecadamantane component (molecular weight 508) eluting at 21.07 min. and the mass spectrum eluting at 21.30 min. The mass spectrum of the methyl undecadamantane component (molecular weight 522).

Figure 93 is a graph illustrating distillation cuts for a feedstock containing higher diamondoids (Feedstock B, atmospheric distillation residue), showing cut selection to favor the enrichment of specific groups of higher diamondoids.

Figure 94 shows the helical structure (right-handed orientation) of [12341]hexamantane.

Detailed Description of the Invention

This detailed description is given in the following subsections:

definition

Advanced diamondoid

Raw material (feedstock)

Isolation process

application

Example

definition

As used herein, the following terms have the following definitions:

The term diamondoid refers to substituted and unsubstituted cage compounds of the adamantane series, which includes adamantane, diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, Octamantane, nonamantane, decamantane, undecamantane, etc., but also all their isomers and stereoisomers. The substituted diamondoids preferably comprise 1 to 10 and more preferably 1 to 4 alkyl substituents.

The term lower diamondoid component or adamantane, diamantane and triamantane component refers to any and/or all unsubstituted and substituted derivatives of adamantane, diamantane and triamantane.

The term "higher diamondoid component" refers to any and/or all substituted and unsubstituted diamondoids corresponding to tetramantane and higher adamantane, including tetramantane, pentamantane, hexamantane alkanes, heptamantanes, octamantanes, nonamantanes, decamantanes, undecamantanes, etc., and include all their isomers and stereoisomers. Preferably, higher diamondoids include substituted and unsubstituted tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane and undecamantane. Figure 2 is a table showing representative higher diamondoids and their molecular weights. The terms "diamondoid family", "tetraadamantane family" and the like are used to define a group of similar diamondoid components having the same number of diamond lattice cage units.

The term "tetramantane component" refers to any and/or all substituted and unsubstituted adamantanes corresponding to tetramantane.

The term "pentamantane component" refers to any and/or all substituted and unsubstituted diamondoids corresponding to pentamantane.

The term "non-ionized diamondoid component" refers to a higher diamondoid component that does not carry a charge such as a positive charge generated during mass spectrometry, wherein the phrase "higher diamondoid component" has the same meaning as defined herein.

The term "non-ionizing tetramantane component" refers to a tetramantane component that does not carry a charge, such as a positive charge generated during mass spectrometry.

The term "non-ionizing pentamantane and higher than pentamantane components" refers to pentamantane components and higher than pentamantane higher diamondoid components.

The term "selected higher diamondoid component" and like terms refer to one or more substituted or unsubstituted higher diamondoids that are desired to be isolated or enriched in the product.

The term "non-selected higher diamondoid components" and similar terms refer to those higher diamondoids that do not belong to the "selected higher diamondoids".

The term "enriched", when used to describe the state of purity of one or more higher diamondoid components, means that such material is at least partially separated from the feedstock, and for "enriched" individual higher The diamondoid component, concentrates at least 25 times and preferably at least 100 times the initial concentration shown in the feedstock. Preferably, "enriched" higher diamondoids or components of "enriched" higher diamondoids constitute at least 25%, especially at least 50% (i.e., 50-100%) of the total material in which they are present , more preferably at least 75% and still more preferably at least 95% or even at least 99% (by weight), or in other words exhibiting at least 25%, 50%, 75%, 95% or 99% of such substances weight purity.

The term "feedstock" or "hydrocarbon-containing feedstock" refers to a hydrocarbonaceous material comprising recoverable amounts of higher diamondoids. Preferably, such feedstocks include oils, gas condensates, refinery streams, oils produced from reservoir rock formations, oil shales, tar sands, and mature source rocks, among others. Such components typically, though not necessarily, include one or more lower diamondoid components as well as non-diamondoid components. The latter are typically characterized as comprising components boiling below and above the lowest boiling 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 inorganic substances. They may also contain those heteromolecules containing sulfur, nitrogen, and the like. All such non-diamondoid species are included in the non-diamondoid component, as that term is defined herein.

The term "non-selected substances" refers to a collection of feedstock components that do not belong to "selected higher diamondoids" and includes "non-diamondoid components", "lower diamondoids" and "non-selected higher diamondoids". Hydrocarbons", these terms are defined here.

The term "remove" or "removing" refers to the process of removing non-diamondoid components and/or lower diamondoid components and/or non-selected higher diamondoid components from a feedstock. Such methods include, by way of example only, particle isolation techniques, distillation, evaporation (at atmospheric or reduced pressure), wellhead separators, adsorption, chromatography, chemical extraction, crystallization, and the like. For example, Chen et al ^{. 4} disclose a distillation process for the removal of adamantanes, substituted adamantanes, diamantanes, substituted diamantanes, and triamantanes from hydrocarbon-containing feedstocks. Particle separation techniques include membrane separation, molecular sieves, gel permeation, size chromatography, and more.

The term "distillation" or "distilling" refers to a fractional distillation process in which species are separated based on differences in vapor pressure, with higher vapor pressure species being collected overhead. Distillation can be performed on hydrocarbonaceous feedstocks and on fractions obtained during the processing of hydrocarbonaceous feedstocks. In this regard, distillation is most commonly carried out under vacuum, but can be at atmospheric pressure or even under elevated pressure.

The terms "fractionation" and "fractionating" refer to methods in which various species in a mixture are separated from each other by, for example, different solubilities, different vapor pressures, different chromatographic affinities, and the like.

The terms "pyrolysis" and "thermal treatment to pyrolysis" and like terms refer to the atmospheric, reduced or elevated heating of a feedstock or feedstock fractions to thermally degrade a portion of one or more components of the feedstock.

The term "non-diamondoid components of a feedstock" refers to components of a feedstock or feedstock fraction that do not have diamondoid properties, wherein the term "diamondoid" is as defined herein.

The term "retention" refers to the 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. In a preferred embodiment, at least about 10% by weight of the higher diamondoid component remains in the recovered feedstock; more preferably, at least about 50% by weight of the higher diamondoid component remains in the recovered feedstock; and more preferably , at least about 90 wt% of the higher diamondoid components remain in the recovered feedstock; each based on the total amount of such diamondoids determined in the feedstock prior to processing.

The term "chromatography" refers to any of a number of well-known chromatographic techniques including, by way of example only, column or gravimetric chromatography (normal or reversed phase), gas chromatography, high performance liquid chromatography law, wait.

The term "alkyl" refers to straight and branched chain saturated aliphatic groups (lower alkyl groups) typically having 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, and typically 3 to 20 carbon atoms and preferably cyclic saturated aliphatic groups (also lower alkyl groups) of 3 to 6 carbon atoms. The terms "alkyl" and "lower alkyl" can be represented by such groups as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, n-heptyl, octyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are exemplified.

Advanced diamondoid

As shown in Figure 1, higher diamondoids are bridged ring naphthenes with a framework of carbon atoms that can superimpose onto the diamond lattice (Figures 1 and 4). They are tetramers, pentamers, hexamers, heptamers, octamers, nonamers, decamers of _adamantane (tricyclo[ ^3.3.1.13,7 ]decane) or _C10H16 etc., wherein each adamantane unit is face-fused. Higher diamondoids can contain many alkyl substituents. These compounds have extremely rigid structures and have the highest stability of any compound represented by their general formula. Four tetramantane structures exist (Figures 2 and 3); iso-tetramantane [1(2)3], anti-tetramantane [121] and skew-tetramantane [123 ] (Figure 3), with the more general designations of these diamondoids given in square brackets according to the convention of Balaban et al. ¹⁵ There are ten pentamantanes ( _Figure 5), nine of which have the formula _C26H32 (molecular weight 344), and of these nine there are three pairs identified by [12(1)3], [1234], [1213 ], and also non-enantiomer pentamantanes represented by [12(3)4], [1(2,3)4], [1212]. There is also the more strained pentamantane represented by the formula _C25H30 (molecular weight ₃₃₀ ), [1231]. See Figure 4. There are thirty-nine different structures of hexamantane ₍ Figure 6), twenty-eight have the molecular formula _C30H36 (molecular weight 396) and of these, six are achiral; ten more strained hexamantane Alkanes have the molecular formula C ₂₉ H ₃₄ (molecular weight 382) and the remaining hexamantane [12312] has the molecular formula C ₂₆ H ₃₀ (molecular weight 342), also known as cyclohexamantane because of its highly condensed circular structure. Heptamantane is postulated to exist in one hundred and sixty possible structures; eighty-five of these have the molecular formula _C34H40 (molecular weight 448) ( _Figure 7) and of these, seven are achiral and have no enantiomers body. Only one of each of the two enantiomeric structures of chiral heptamantane is shown in FIG. 7 . Of the remaining heptamantanes, sixty-seven have the formula C ₃₃ H ₃₈ (molecular weight 434) and six have the molecular formula C ₃₂ H ₃₆ (molecular weight 420). These two heptamantane families have those structures that show greater internal bond strain, have correspondingly lower stability and are not shown in FIG. 7 . The remaining two have the molecular formula C ₃₀ H ₃₄ (molecular weight 394) ( FIG. 7 ). Octamantanes have eight "diamond crystal cage units" and exist in five families of core structures of different molecular weights (Figure 2). Among the octamantanes, eighteen have the molecular formula C ₃₄ H ₃₈ (molecular weight 446). Figure 8 shows each of the 446 molecular weight octamantane isomers. Other octamantanes have _the molecular formula _C38H44 (molecular weight 500). The remaining octamantane families, C ₃₇ H ₄₂ (MW 486), C ₃₆ H ₄₀ (MW 472) and C ₃₃ H ₃₆ (MW 432) show greater bond strain and correspondingly lower stability. Nonamantanes exist in six families of different molecular weights with the following molecular formulas: C ₄₂ H ₄₈ (MW 552), C ₄₁ H ₄₆ (MW 538), C ₄₀ H ₄₄ (MW 524), C ₃₈ H ₄₂ (MW 498), C ₃₇ H ₄₀ (molecular weight 484) and C ₃₄ H ₃₆ (molecular weight 444). In addition, decamantane exists in seven families of different molecular weights. Among the decamantanes, there is a single decamantane having the molecular formula C ₃₅ H ₃₆ (molecular weight 456), which is structurally dense and has low internal bond strain relative to other decamantanes. Another decamantane family has molecular formulas: C ₄₆ H ₅₂ (MW 604), C ₄₅ H ₅₀ (MW 590), C ₄₄ H ₄₈ (MW 576), C ₄₂ H ₄₆ (MW 550), C ₄₁ H ₄₄ ( MW 536) and C ₃₈ H ₄₀ (MW 496). Undecadamantane (Figure ₁₁ ) as molecular formula _C50H56 (MW ₆₅₆ ), _C49H54 (MW 642 _{) , C48H52 (} MW 628), _C46H50 (MW 602), _C45H48 (Molecular weight 588), C ₄₂ H ₄₄ (Molecular weight 548), C ₄₁ H ₄₂ (Molecular weight 534), C ₃₉ H ₄₀ (Molecular weight 508). More and less preferred higher diamondoids (Fig. 2) are based on their internal bond strain and corresponding stability as reflected by their relative concentrations in the various feedstocks.

raw material

The higher diamondoids provided by the present invention exist only in dilute concentrations in solution in petroleum feedstocks.

In the process of the present invention, the feedstock is selected such that the feedstock includes recoverable amounts of one or more selected higher diamondoid components. Preferably, such feedstocks include at least about 1 ppb of one or more higher diamondoid components, more preferably, at least about 25 ppb and even more preferably at least about 100 ppb. Of course, it will be appreciated that feedstocks with higher concentrations of higher diamondoid components facilitate recovery of these components.

Preferred feedstocks include, for example, natural gas condensates and refinery streams with high concentrations of higher diamondoids. For the latter, such refinery streams include hydrocarbonaceous streams that may be recovered from cracking processes, distillation, coking, etc. Particularly preferred feedstocks include gas condensates recovered from the Norphlet formation in the Gulf of Mexico and from the LeDuc formation in Canada.

In one embodiment, the feedstock used in the process of the present invention typically includes non-diamondoid components boiling both below and above the lowest boiling higher diamondoid components selected for recovery and a One or more lower diamondoid components. These feedstocks usually contain mixtures of higher diamondoids. Depending on the selected higher diamondoids, some of these higher diamondoids have lower boiling points than the selected higher diamondoids. Typically, the lowest boiling higher diamondoid component selected for recovery has a boiling point greater than about 335°C. In a typical feedstock, the concentration ratio of lower diamondoids to higher diamondoids is usually about 250:1 or higher. Furthermore, as illustrated in Figure 18, typical feedstocks that include higher diamondoid components also include non-diamondoid components.

In such feedstocks, the selected higher diamondoid components are often not efficiently recovered directly from the feedstock because of their low concentration relative to the non-selected components. Accordingly, the process of the present invention is capable of removing sufficient amounts of these contaminants from feedstocks under those conditions that provide a processed feedstock capable of recovering selected higher diamondoid components therefrom.

Separation method

A general isolation method for higher diamondoids is shown in FIG. 12 .

In one embodiment, removal of contaminants includes distillation of the feedstock to remove non-diamondoid components, as well as lower diamondoid components and in some cases other non-selective higher diamondoids, the latter having a low boiling point Based on the boiling point of the lowest boiling higher diamondoid selected for recovery.

In a particularly preferred embodiment, the feedstock is distilled to provide cuts above and below about 335°C, atmospheric pressure equivalent boiling point and, more preferably, above and below about 345°C atmospheric pressure equivalent boiling point. In either case, the lower-boiling cuts (which are enriched in the lower diamondoids) and the low-boiling non-diamondoid components are drawn overhead and discarded, and the higher-boiling cuts (which are enriched in the higher-order diamondoids) are drawn overhead and discarded. diamondoids) are retained. It will of course be understood that cut point temperatures during distillation are a function of pressure and the above temperatures are referenced to atmospheric pressure. A reduced pressure will result in a lower distillation temperature required to achieve the same cut point, while an increased pressure will result in a higher distillation temperature to achieve the same cut point. The pressure/temperature correlation of atmospheric distillation and reduced pressure or elevated pressure distillation is well known to those skilled in the art.

A distillation operation can be performed to fractionate the feedstock and provide several cuts in the desired temperature range to achieve an initial enrichment of the selected higher diamondoids or groups of selected higher diamondoids. Cuts enriched in one or more selected diamondoids or a desired specific diamondoid fraction remain and require further purification. The table below illustrates representative cut points for enriching the various higher diamondoids in the overhead. In practice, it is desirable to produce cuts over a wider temperature range, which often contain groups of higher diamondoids that can be separated together in subsequent separation steps.

cut point most preferred Preferred Advanced diamondoid Lower cut temperature (°C) Higher cut temperature (°C) Lower cut temperature (°C) Higher cut temperature (°C) Tetramantane 349 382 330 400 Pentamantane 385 427 360 450 Cyclohexamantane 393 466 365 500 Hexamantane 393 466 365 500 Heptamantane 432 504 395 540 Octamantane 454 527 420 560 Nonamantane 463 549 425 590 Decamantane 472 571 435 610 undecamantane 499 588 455 625 useful   Advanced diamondoid Lower cut temperature (°C) Higher cut temperature (°C) Tetramantane 300 430 Pentamantane 330 490 Cyclohexamantane 330 550 Hexamantane 330 550 Heptamantane 350 600 Octamantane 375 610 Nonamantane 380 650 Decamantane 390 660 Undecamantane 400 675

It will be appreciated that substituted higher diamondoids thus shift these preferred cut point temperatures to higher temperatures due to the increase in substituent groups. Additional temperature refining makes it possible to obtain higher purity cuts of the desired diamondoids. Figure 93 provides a further illustration of how fractionation can provide cuts enriched in single or multiple higher diamondoid components.

It is further understood that fractionation can be stopped before the selected higher diamondoids are withdrawn overhead. In this case the higher diamondoids can be isolated from the fractionation bottoms.

Other methods of removal of lower diamondoids, unselected higher diamondoids, if any, and/or hydrocarbon-containing non-diamondoid components include, by way of example only, particle separation techniques, at atmospheric or reduced pressure Evaporation under pressure, crystallization, chromatography, wellhead separator, decompression, etc. The removal method is able to utilize larger size higher diamondoids to separate lower diamondoids from them. For example, particle separation techniques using membranes allow the feedstock retained in the membrane to selectively allow lower diamondoids to pass through the membrane barrier, as long as the pore size of the membrane barrier is selected to have higher diamondoid components (compared with lower diamondoids). Distinguish between compounds of the size of hydrocarbon components vs. The pore size of molecular sieves such as zeolites can also be used for particle separation.

In a preferred embodiment, the removal process is provided for a treated feedstock having a ratio of lower adamantane component to higher adamantane component 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 removing the lower diamondoid component from the feedstock, at least about 10%, more preferably at least 50% and even more preferably at least 90% of the higher diamondoid component remains in the feedstock Quantity comparison previously determined in raw materials.

When recovery of the hexamantane and higher diamondoid components is desired and when the feedstock contains non-diamondoid contaminants, the feedstock is also typically subjected to pyrolysis so that the hydrocarbon-containing non-diamondoids are removed from the feedstock. At least a portion of the hydrocarbon component. This pyrolysis effectively concentrates the amount of higher diamondoids in the pyrolytically treated feedstock, thereby enabling their recovery (Figure 18).

By heating the feedstock under vacuum or in an inert atmosphere at a temperature of at least about 390°C and preferably, about 400 to about 550°C, more preferably about 400 to about 450°C, and especially 410 to 430°C for a period of time such that Pyrolysis is performed by pyrolyzing at least a portion of the non-diamondoid component of the feedstock. The particular conditions used are chosen such that recoverable amounts of the selected higher diamondoid components remain in the feedstock. The choice of such conditions is within the common knowledge of a person skilled in the art.

Preferably, the pyrolysis is carried out for a sufficient duration and at a temperature high enough that at least about 10% (more preferably at least about 50% and even more) of the non-diamondoid components in the pyrolysis-treated feedstock Preferably at least about 90%) thermally degrades, based on the total weight of non-diamondoid components in the feedstock prior to pyrolysis.

In another preferred embodiment, after pyrolysis of the feedstock, at least about 10%, more preferably at least about 50%, and more preferably at least about 90% of the higher diamondoid component remains in the feedstock after pyrolysis treatment , compared with the amount measured in the feedstock before pyrolytic treatment.

In a preferred embodiment, the removal of lower diamondoids and low-boiling hydrocarbon-containing non-diamondoid components from the feedstock may be performed prior to pyrolytic treatment. However, it is understood that the order of these procedures may be reversed so that pyrolysis occurs prior to removal of lower diamondoids from the feedstock.

This pyrolysis procedure, although a preferred embodiment, is not always necessary. This is attributed to the fact that the concentration of higher diamondoids is high enough in some feedstocks that the processed feedstock (after removal of lower diamondoid components) can be used directly in purification techniques such as chromatography, crystallization, etc. To obtain higher diamondoid components. However, when the concentration or purity of the higher diamondoid components in the feedstock is not at a level where recovery is possible, then the pyrolysis step should be used.

Even when pyrolysis is used, it is preferred to further purify the recovered feedstock by using one or more purification techniques such as chromatography, crystallization, thermal diffusion techniques, zone refining, stepwise recrystallization, particle separation, and the like. In a particularly preferred method, the recovered starting material is first analyzed by gravity column chromatography using silver nitrate impregnated silica gel, followed by HPLC using two different columns with different selectivities to isolate the selected diamondoids, and crystallization In order to obtain highly concentrated crystals of target higher diamondoids. When the concentration of higher diamondoids is not high enough for crystallization to occur, further concentration, for example by preparative capillary gas chromatography, is required.

Enantioselective (chiral) stationary phases have been used in chromatography for further separations. HPLC methods also offer the possibility to achieve resolution of enantiomers using chiral solvents or additives.

For example, separation of the enantiomers of higher diamondoids can be achieved using several approaches. One such route is spontaneous crystallization with both resolution and mechanical separation. This route to enantiomeric resolution can be enhanced by the 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 methods of enantiomeric resolution include chiral separations, which can be performed using gas chromatography (GC), see "Chiral Chromatography", T.E. Beesley et al., Wiley, Johnson & Sons, January 1998, Incorporated here by reference, by high performance liquid chromatography (HPLC) and by supercritical fluid chromatography (SFC) techniques, see "Supercritical fluids in Chromatography and Extraction", R.M.Smith, Elsevier Science, December 1997, incorporated herein for use refer to.

application

The method of the present invention provides a composition enriched in higher diamondoids. These higher diamondoids are useful in micro- and molecular-electronics and nanotechnology applications. In particular, the rigidity, strength, stability, thermal conductivity, diversity of structural forms and multiple attachment sites exhibited by these molecules make it possible to precisely construct robust, durable precision devices at the nanometer scale. Figure 15 shows the size and shape of selected higher diamondoids relative to the molecular components (Buckminsterfullerene and carbon nanotubes) in the development of molecular electronic devices.

The higher diamondoids are three-dimensional nano-sized units that exhibit different diamond-type lattice arrangements. This translates into a wide variety of shapes and sizes for these extremely rigid nanostructures, for example, [121(3)4] hexamantane is "T" shaped, [12134] is "L" shaped, and [1 (2)3(1)2] are flattened with four lobes. [12(3,4)12]heptamantane has a cross-shaped structure, while [121234] is an "L" shape. [12312] Hexamantane has a disc-shaped structure. [121321] Heptamantane is discoid with one coplanar lobule, while [1213(1)21] octamantane is discoid with two opposing coplanar lobes. [1232(1)3] Octamantanes are wedge-shaped. [121(2)32(1)3]nonamantane has a triangular sheet structure. [1231241(2)3] Decadamantane is a perfect octagon, while [121231212] Decadamantane is a rectangular plate-shaped structure. [123(1,2)42143] Undecadamantane is an extended pyramid. Among the higher diamondoids there are many other shapes that can be used in nanotechnology and nanostructured materials, depending on the specific geometry. The carbon-frame structures of tetraamantane to undecamantane are shown in FIGS. 3 to 11 .

Higher diamondoids also include a series of rod-shaped structures of different lengths. Tetramantane with the sequence "121" is the first member of this family of rod-shaped structures, [1212] pentamantane is next, followed by [12121] hexamantane, and so on. Each additional diamond cage increases the length of the rod by about 0.3 nanometers, where [1212]pentamantane has a length of about 1.1 nanometers.

The [1(2)3]tetramantane begins a series of denser, flat-topped, pyramidal structures (Fig. 3). [1(2,3)4]pentamantane (Fig. 5) continues this trend and is a perfect tetrahedral pyramid.

Higher diamondoids also include helical structures of various lengths. The first chiral diamondoid was the tetraadamantane with the sequence 123. We have assigned the two enantiomers of 123 tetramantane as A and B. Their structures can also be represented by the sequences 123 and 124 by a modification of the Balaban nomenclature. These two diamondoids have left-handed (counterclockwise), i.e., tetramantane A, and right-handed (clockwise) (tetramantane B)-helix (helix) linear or helical (screw) structures, both Represents a partially bent portion of a helix. Unfortunately, the Balaban nomenclature does not provide a way of specifying the left and right helical forms, only that there are two forms. This sequence continues with continuations 1234 and 1243 (ie, A and B) for pentamantane (FIG. 5), 12341 and 12431 (again, A and B) for hexamantane (FIG. 6), and so on. The hexamantane members complete a full rotation of the right-handed and left-handed helices of these helical nanostructures (FIG. 94).

These specific structural properties distinguish higher diamondoids from acyclic molecules, from condensed-ring systems and even from bridged-ring counterparts. Large stability, nanoscale size, variable yet rigid geometry, well-defined distances of connection sites, and non-planar bridgeheads lead to their uniqueness. Due to the rigidity, specific geometry, 3D shape and nanometer size of the higher diamondoid components, it is foreseeable that aggregation of molecules and the inclusion of their building blocks will enable the construction and synthesis of unprecedented arrays of desired materials such that The material could be used in molecular electronic computing devices, small machines such as molecular-scale robots and self-replicating manufacturing systems. Additionally, the higher diamondoids can be used as novel structural materials with special chemical, optical, electronic, and thermal conductivity properties for coatings, film coatings, and other applications utilizing diamond-like properties, among others. New uses of materials containing higher diamondoids in the field of microelectronics are disclosed. Embodiments include, but are not limited to, thermally conductive films in integrated circuit packaging, low-k dielectric layers in integrated circuit interconnects, thermally conductive adhesive films, thermally conductive films in thermoelectric cooling devices , passivation film for integrated circuit devices (IC), and field emission cathodes.

In addition, these advanced diamondoids can also be used in high quality lubricating fluids which exhibit high viscosity indices and very low pour points. ¹³ When so used, these fluids include fluids of lubricating viscosity and fluids of about 0.1-10 wt% diamondoid.

In addition, these higher diamondoids can be used as high density fuels in the manner of Chung et al. ¹⁴ (which is hereby incorporated by reference).

The following examples are given for the purpose of illustrating the invention, but are in no way considered to limit the scope of the invention. All temperatures are in degrees Celsius unless otherwise indicated.

Example

The following abbreviations used herein and in the drawings have the following meanings: Any abbreviation not defined below has its generally accepted meaning.

API = American Petroleum Institute

atm eqv = atmospheric equivalent (atmospheric equivalent)

btms = bottoms

EOR Traps = end of run traps

Fid＝ flame ionization detector

g= grams

GC = gas chromatography

GC/MS = gas chromatography/mass spectrometry

h = hour

HPLC = high performance liquid chromatography

HYD RDG ＝hydrometer reading

L = liter

min= minute

mL= milliliter

mmol = millimole

N = Equivalent concentration (normal)

pA = pico amps

ppb= one billionth (parts per billion)

ppm= one millionth (parts per million)

RI = Refractive index

SIM DIS = simulated distillation

ST = start

TIC = total ion current

TLC = thin layer chromatography

VLT＝ steam line temperature (vapor line temperature)

VOL PCT = volume percentage

v/v = ratio of volume to volume

wt = weight

WT PCT = weight percent

introduce

The steps used in the various examples are shown diagrammatically in FIG. 12 .

Example 1 describes the most general approach to the isolation of higher diamondoid components that can be applied to all feedstocks. This method uses HPLC (step 7, Figure 12) as its final isolation step.

Example 2 describes a modification of the method of Example 1 in which preparative gas chromatography (step 7', Figure 12) replaces HPLC as the final isolation step.

Example 3 describes a modification of the method of Example 1 in which pyrolysis (step 5, Figure 12) is omitted. As optionally shown in Figure 12, the liquid chromatography step (step 6, Figure 12) was also omitted. These variations are generally only applicable to the chosen feedstock and generally when tetramantane, pentamantane and cyclohexamantane are the higher diamondoids of interest.

Example 4 describes another process variant in which the final products of examples 1 and 3 are purified by preparative gas chromatography in order to achieve a further purification of higher diamondoid components (step 8, Figure 12).

Example 5 describes the enrichment and separation of tetramantane components.

Example 6 describes the enrichment and isolation of pentamantane components.

Example 7 describes the enrichment and isolation of the hexamantane component.

Example 8 describes the enrichment and isolation of the heptamantane component.

Example 9 describes the enrichment and isolation of octamantane components.

Example 10 describes the enrichment and isolation of nonamantane components.

Example 11 describes the enrichment and separation of decamantane components.

Example 12 describes the enrichment and isolation of the undecadamantane component.

It will be appreciated that it is possible to vary the order of the individual distillation, chromatography and pyrolysis steps, although the order listed in Example 1 gave the best results.

Example 1

This embodiment has seven steps (see flow chart in Figure 12).

Step 1. Raw material selection

Step 2. GC/MS Analysis

Step 3. Atmospheric distillation of raw materials

Step 4. Vacuum Fractional Distillation of Atmospheric Distillation Residue

Step 5. Pyrolysis of the isolated fraction

Step 6. Removal of Aromatic and Polar Non-Diamondoid Components

Step 7. Multi-column HPLC separation of higher diamondoids

a) The first column of the first selectivity provides a fraction enriched in specific higher diamondoids.

b) A second column of different selectivity provides isolated higher diamondoids.

This example is written in terms of isolating several hexamantanes. As shown in Examples 5-12, it can be readily adapted to isolate other higher diamondoids.

Step 1 - Raw material selection

Obtain suitable starting materials. These raw materials include gas condensates, Feedstock A (Figure 16) and gas condensates containing petroleum components, Feedstock B. Although other condensates, petroleum, or refinery fractions and products could be used, these two raw materials were chosen because of their high diamondoid concentrations, about 0.3 wt% higher diamondoids, determined by GC and GC/ As determined by MS. Both raw materials have a light color and have an API gravity between 19 and 20° API.

Step 2 - GC/MS analysis

Feedstock A was analyzed by using gas chromatography/mass spectrometry to confirm the presence of target higher diamondoids and to provide gas chromatographic retention times for these target species. This information was used to track each target higher diamondoid during subsequent isolation procedures. Figure 13A is a table listing typical GC/MS analytical information (GC retention time, mass spectral molecular ion (M+) and base peak) for hexamantane. This table (FIG. 13A) also contains similar GC/MS analytical information for other higher diamondoids. While relative GC retention times are approximately constant, non-reference GC retention times vary over time. It is recommended that GC/MS analytical values be revised periodically, especially when GC retention time shifts are detected.

Step 3 - Atmospheric Distillation of Raw Materials

The sample of feedstock B was distilled into multiple fractions on the basis of boiling point to separate out low boiling point components (non-diamondoid and lower diamondoid) and to achieve further concentration and enrichment of special higher diamondoid in each fraction. set. The yields of the atmospheric fraction of two independent samples of feedstock B are shown in Table 1 below and compared to simulated distillation yields. It can be seen from Table 1 that the simulated distillation data is consistent with the actual distillation data. The simulated distillation data is used to plan the subsequent distillation process.

      Table 1: Obtained from two separate runs of material B

Yield of Atmospheric Distillation Fraction Cut fraction (°F) Simulated Distillation Estimated Yield (Wt%) Raw material B (test 2) yield (Wt%) difference to 349 8.0 7.6 0.4 349 to 491 57.0 57.7 -0.7 491 to 643 31.0 30.6 0.4 643 and higher 4.0 4.1 -0.1 Cut fraction (°F) Simulated Distillation Estimated Yield (Wt%) Raw material B (test 1) yield (Wt%) difference to 477 63.2 59.3 3.9 477 to 515 4.8 7.3 -2.5 515 to 649 28.5 31.2 -2.7 649 and higher 3.5 2.1 1.4

Step 4 - Fractionation of Atmospheric Distillation Residue by Vacuum Distillation

The obtained feedstock B atmospheric distillation residue from step 3 (2-4 wt% of the original feedstock) was distilled into higher diamondoid-containing fractions, as shown in FIGS. 17 and 93 . The feed to this high temperature distillation process is atmospheric pressure 650°F + bottoms. The complete Feed B distillation results are given in Tables 2A and 2B. Tables 3A and 3B illustrate the distillation results for Feed B 650°F + distillation bottoms.

Table 2A. Distillation Report for Feedstock B

                                   

Columns used: Clean 9”x1.4” Protruded Packed Distillation records normalization actual cut fraction Steam temperature ST-END Weight g Volume ml 60°F API60/60 Density 60°F WT PCT VOLPCT WT PCT VOLPCT 1 226 - 349 67.0 80 38.0 0.8348 7.61 8.54 7.39 8.26 2 349 - 491 507.7 554 22.8 0.9170 57.65 59.12 55.98 57.23 3 491 - 643 269.6 268 9.1 1.0064 30.62 28.60 29.73 27.69 Column retention - 0.2 0 6.6 1.0246 0.02 0.00 0.02 0.00 BTMS 643 + 36.1 35 6.6 1.0246 4.09 3.74 3.98 3.62 EOR TRAPS 0.0 0 0.00 0.00 0.00 total 880.6 937 100.00 100.00 97.09 96.80 Loss (LOSS) 26.4 31 2.91 3.20 Feed (FEED) 907.0 968 19.5 0.9371 100.00 100.00 Back calculated API and density 19.1 0.9396

Table 2B: Distillation Report for Feedstock B

Raw material B

Columns used: Clean 9”x1.4” Protruded Packed Temperature °F pressure reflow cut fraction Volume ml 60°F Weight g API proportion steam Can support ratio NO observe 60°F VLT ATM EQV. HYD RDG Temperature °F 93 225.8 262 50.000 3:1 start top discharge 198 349.1 277 50.000 3:1 1 80 67.0 39.6 80.0 38.0 321 490.8 376 50.000 3:1 2 554 507.7 24.1 80.0 22.8 Cut 2 looked milky with white crystals forming in the stop line. A heat lamp shines on the dropper. Cool and transfer the residue to a smaller flask. 208 437.7 323 10.000 3:1 start top discharge 378 643.3 550 10.000 3:1 3 268 269.6 9.9 75.0 9.1

downtime due to dry tank Test Collector Terminal 0 0.0 Distilled volume 902 Column retention 0 0.2 0.0 0.0 6.6 residue 35 36.1 7.2 72.0 6.6 Recycle 937 880.6 Feeding 968 907.0 20.7 80.0 19.5 loss 31 26.4

Table 3A: Vacuum Distillation Report for Feedstock B

           Feedstock B - Atmospheric Distillation Residue 650°F + Residue

Columns used: Sarnia Hi Vac Temperature °F pressure reflow cut fraction Volume ml Weight g API proportion steam Can support ratio NO observe 60°F VLT ATMEQV. 60°F HYDRDG Temperature °F 315 601.4 350 5.000 start top discharge 344 636.8 382 5.000 300 reading 342 644.9 389 4.000 500 reading 344 656.3 395 3.300 1 639 666.4 7.8 138.0 4.1 353 680.1 411 2.500 400 reading 364 701.6 430 2.100 2 646 666.9 9.4 138.0 5.6 333 736.0 419 0.400 200 reading 336 751.9 432 0.300 3 330 334.3 12.4 139.0 8.3 391 799.9 468 0.500 4 173 167.7 19.0 139.0 14.5 411 851.6 500 0.270 5 181 167.3 26.8 139.0 21.7 460 899.8 538 0.360 6 181 167.1 27.0 139.0 21.9 484 950.3 569 0.222 7 257 238.4 26.2 139.0 21.2 Distillation was turned off to check the tank temperature limits for the customer. Discharged collector material 5.3 g) 472 935.7 576 0.222 start top discharge 521 976.3 595 0.340 8 91 85.4 23.7 139.0 18.9 527 999.9 610 0.235 9 85 80.8 23.0 139.0 18.2 527 1025.6 624 0.130 10 98 93.8 21.6 139.0 16.9 16.5 grams of residual collector material discharged (~4 grams of water) MIDAND Test Collector Terminal 20 17.8 (math merge) Distilled volume 2701 Column retention 4 4.0 0.0 0.0 3.4 residue 593 621.8 11.0 214.0 3.4 Recycle 3298 3311.7 Feeding 3298 3326.3 18.0 234.0 8.6 loss -5 14.6

Table 3B: Distillation Report for Feedstock B - Residue

       Material B - Atmospheric Distillation Residue 650°F + Residue

Columns used: Sarnia HiVac cut fraction steam temperature weight volume APIs density WT VOL WT VOL ST - END G ml 60°F 60/60 60°F PCT PCT PCT PCT 1 601 - 656 666.4 639 4.1 1.0435 20.12 19.38 20.03 19.40 2 656 - 702 666.9 646 5.6 1.0321 20.14 19.59 20.05 19.62 3 702 - 752 334.3 330 8.3 1.0122 10.09 10.01 10.05 10.02 4 752 - 800 167.7 173 14.5 0.9692 5.06 5.25 5.04 5.25 5 800 - 852 167.3 181 21.7 0.9236 5.05 5.49 5.03 5.50 6 852 - 900 167.1 181 21.9 0.9224 5.05 5.49 5.02 5.50 7 900 - 950 238.4 257 21.2 0.9267 7.25 7.79 7.17 7.80 8 950 - 976 85.4 91 18.9 0.9408 2.58 2.76 2.57 2.76 9 976 - 1000 80.8 85 18.2 0.9452 2.44 2.58 2.43 2.58 10 1000 - 1026 93.8 98 16.9 0.9535 2.83 2.97 2.82 2.98 Column retention 4.0 4 3.4 1.0489 0.12 0.12 0.12 0.12 BTMS 1026 + 621.8 593 3.4 1.0489 18.78 17.98 18.69 18.01 EOR TRAPS 17.8 20 0.54 0.61 0.54 0.61 total 3311.7 3298 100.00 100.00 99.56 100.15 loss 14.6 -5 0.44 -0.15 Feed 3326.3 3293 8.6 1.0100 100.00 100.00 Back calculated API and density 9.4 1.0039

Table 4: Elemental composition of raw material B Analysis of Raw Material B 650°F+ Residue Measurement value nitrogen 0.991wt% sulfur 0.863wt% nickel 8.61ppm vanadium <0.2ppm

Table 4 illustrates the partial elemental composition of Feed B atmospheric distillation (650°F) residue containing some of the identified impurities. Table 4 shows the weight percents of nitrogen, sulfur, nickel and vanadium in the Feed B atmospheric distillation residue. Subsequent steps remove these materials.

Step 5 - Pyrolysis of the Isolated Fraction

The high temperature reactor was used to pyrolyze and degrade part of the non-diamondoid components in each distillation fraction obtained in step 4 ( FIG. 12 ), thus enriching the residue in diamondoids. The pyrolysis process was carried out at 450°C for 19.5 hours. The gas chromatogram (FID) of fraction #6 (Table 3B) is shown in Figure 18A. Figure 18B is a chromatogram of pyrolysis products. A comparison of these chromatograms shows that pyrolysis has removed the major non-diamondoid hydrocarbons and has significantly increased the concentration of higher diamondoids, particularly the hexamantane. A 500 mL PARR® reactor obtained from PARR Instrument Company, Moline, Illinois was used for this pyrolysis step.

Step 6 - Removal of Aromatic and Polar Non-Diamondoid Components

The pyrolyzate produced in step 5 was passed through a silica gel gravity chromatography column (using cyclohexane as the eluting solvent) to remove polar compounds and asphaltenes (step 6, Figure 12). The use of silver nitrate impregnated silica gel (10 wt% _AgNO3 ) can provide a cleaner diamondoid-containing fraction by removing free aromatic and polar components. Although an aromatic separation method using this chromatographic analysis is not required, it facilitates later steps.

Step 7 - Multi-column HPLC isolation of higher diamondoids

An excellent method for isolating higher purity diamondoids uses two or more HPLC columns sequentially with different selectivities.

The first HPLC system consisted of two Whatman M2010/50 ODS columns operated in series, using acetone as the mobile phase at a flow rate of 5.00 mL/min. A series of HPLC fractions were taken (see Figure 19). Fractions 36 and 37 were combined and removed for further purification on a second HPLC system. This combined fraction (36 and 37) contained hexamantanes #7, #11 and #13 (Figure 19, see also Figure 13B).

Further purification of this pooled ODS HPLC fraction can be achieved by using a Hypercarb stationary phase HPLC column with different selectivity in the separation of the various hexamantanes, compared to the ODS column discussed above. Figure 20 shows the elution times of various hexamantanes on a Hypercarb HPLC column (acetone as mobile phase).

The difference in elution time and elution order of hexamantanes on ODS and Hypercarb HPLC columns can be seen by comparing these two Figures 19 and 20. For example, hexamantanes #11 and #13 eluted together on the ODS HPLC system (Figure 19), but eluted as separate fractions (fractions 32 and 27, respectively) on the Hypercarb system (Figure 20).

The different elution order and timing of the selected higher diamondoids on these two systems can be used to separate the co-eluting higher diamondoids. It can also be used to remove impurities. By using this method on the combined ODS HPLC fractions 36 & 37, the appropriate Hypercarb HPLC fraction was taken, thus providing high purity hexamantane #13 (Figures 51A and 51B). Additional ODS HPLC fractions and Hypercarb HPLC cuts can be used to isolate the remaining hexamantane. This isolation strategy is also applicable to other higher diamondoids, although the elution solvent composition can be changed.

ODS and Hypercarb columns can also be used in reverse order for these isolations. Using a method similar to the above, ie utilizing a Hypercarb or other suitable column to fractionate the hexamantane-containing ODS fraction and collect at corresponding elution times, can result in the isolation of the remaining hexamantane in high purity. This is also true for the other higher diamondoids from tetramantane to undecamantane, including substituted forms.

Example 2

Steps 1, 2, 3, 4, 5 and 6 of Example 1 were repeated (Fig. 12). The following variation of step 7 was performed.

Step 7':

A double-column preparative capillary gas chromatograph was used to isolate hexamantane from the product of Example 1, Step 6. For the first preparative capillary GC column, methylsiloxane DB-1 equivalent, six The cut-off time of adamantane. The results are shown in Figure 42A. Two cuts identified as "Cut and Peak Sent to Column 2" were taken which contained two of the hexamantane components from Feed B. The preparative capillary gas chromatograph used was manufactured by Gerstel, Inc., Baltimore, Maryland, USA.

The first column is used to concentrate the higher diamondoids, such as hexamantanes, by taking cuts before passing to the second column (see Figure 42B for illustration of hexamantanes #2 and #8). A second column, phenyl-methylsiloxane, DB-17 equiv., was used to further isolate and purify the hexamantanes before isolating the desired peaks and retaining them in each collector (collectors 1-6) . GC collector fraction 1 contained crystals of hexamantane #2. GC collector fraction 3 contained crystals of hexamantane #8. Subsequent GC/MS analysis of collector #1 material (Figure 43A and B) showed it to be high purity hexamantane #2, based on GC/MS analysis from Step 2. Similarly, GC analysis of collector #3 material (Figure 44A and B) showed it to be primarily hexamantane #8. Micrographs of hexamantane #2 and #8 crystals (analyzed in Figures 43 and 44) are shown in Figures 45 and 46. This procedure was repeated to isolate other hexamantanes. This is also true for other higher diamondoids.

Example 3

Steps 1, 2, 3, and 4 of Example 1 were repeated using starting material A (FIG. 12). Feedstock A may be particularly low in non-diamondoids in the atmospheric distillation residue fraction recovered in step 4. The pyrolysis step (5) of Example 1 can be omitted, especially when the higher diamondoids sought are tetramantane, pentamantane and cyclohexamantane. In this case, the fraction separated in step 4 was sent directly to steps 6 and 7 of example 1 or directly to step 7 of example 2 (Figure 12). This process variant can likewise be applied to the low-boiling tetramantane-containing fraction of starting material B. However, pyrolysis is highly desirable when larger amounts of non-diamondoid components are present.

From this feed a fraction corresponding in cut point to Fraction #1 of Step 4 was taken (see Distillation, Table 3, Example 1 and Figure 17). This fraction was further fractionated by preparative capillary gas chromatography similar to the process shown in step 7' of Example 2 (Figure 12).

A two-column preparative capillary gas chromatograph was then used to isolate the target tetramantane from the distillate fraction purified by column chromatography (step 6, Figure 12). Target diamondoids (e.g., Tetramantane) cut-off time. These results are shown at the top of Figure 21, designated as cuts 1, 2 and 3.

The first column is used to concentrate the target diamondoid (e.g., tetramantane) by taking a cut, which is then sent to a second column (phenyl-methylsiloxane, DB-17 equivalent) (see bottom of Figure 21 ). A second column further separates and purifies the target diamondoids before sending them to the respective collectors (collectors 1-6). GC collectors 2, 4 and 6 contained selected tetramantanes (Figure 21).

The highly concentrated tetramantane higher diamondoids are then crystallized in the collector or dissolved and recrystallized from solution. Under a microscope at 3OX magnification, crystals of tetramantane were visible in preparative GC collectors 2, 4 and 6 (see Figure 22). Further concentration by preparative GC is required when the concentration is not high enough for crystallization to occur. This method can also be used to isolate other higher diamondoids from feedstock A.

Example 4: Preparative GC of HPLC fractions

For heptamantane, octamantane and higher diamondoids, etc., it is desirable to further fractionate the HPLC product obtained in Example 1, step 7. This was performed by using preparative capillary gas chromatography as described in Example 2, step 7'.

The following higher diamondoid components were isolated and crystallized: all tetramantane from both feedstocks A and B, all pentamantane (molecular weight 344) isolated from feedstock B; two hexamantane crystals isolated from feedstock B (molecular weight 396); two heptamantane crystals (molecular weight 394) isolated from raw material B, and octamantane crystals (molecular weight 446) isolated from raw material B. And nonamantane crystals (molecular weight 498) and decamantane crystals (molecular weight 456) isolated from raw material B. Other higher diamondoid components can also be isolated by using the procedures described in these examples.

Example 5A: Isolation of tetramantane

The general method of Examples 1 and 2 was used to enrich and isolate the tetramantane.

In this example, pyrolysis step 5 (Figure 12) was not used and the product of step 4 was sent directly to column chromatography (step 6 of Example 1). The product was purified by column chromatography and then worked up as follows:

The eluate from the column chromatography analysis of step 6 was analyzed by GC/MS to determine the approximate GC retention times of tetramantane isomers. Individual tetramantanes are numbered according to their elution order in GC/MS analysis. This reference number is used to distinguish the various tetramantanes in subsequent steps. It must be noted that the enantiomeric pairs in this analysis were not resolved and therefore these enantiomers (racemic mixtures) were given individual numbers for this purpose. GC retention times can vary with changing column and GC conditions, as needed by using this procedure to prepare new reference retention time tables. Below is the table used in the procedure of Example 5D below.

Tetramantane reference number# 1 2 3 GC/MS Retention time (Min.) 11.28 11.84 12.36

A two-column preparative capillary gas chromatograph was then used to isolate tetramantanes from the distillate fraction purified by column chromatography. The results are shown in Figure 21, designated as cuts 1, 2 and 3.

The first column was used to concentrate the tetramantanes by taking cuts before passing to the second column (see Figure 21). A second column, phenyl-methylsiloxane, DB-17 equiv., further isolates and purifies the tetramantanes before sending them to each vial (collectors 1-6). GC collector fractions 2, 4 and 6 were collected for further processing.

Highly concentrated tetramantane is then crystallized from solution. Under a microscope at 3OX magnification, crystals were visible in preparative GC collector fractions 2, 4 and 6 (see Figure 22). Further concentration by preparative GC is required when the concentration is not high enough for crystallization to occur. 22A, B, and C illustrate microscopic images of tetramantane crystals isolated from feedstock A in collectors #2, #4, and #6 (corresponding to tetramantane #1, #2, and #3, respectively). photo.

After obtaining crystals of the appropriate size, the material was sent for structure determination using X-ray diffraction. The enantiomeric tetramantanes can be further separated to resolve their two components, as described above.

Example 5B: Enrichment of tetramantane using pyrolysis

This example shows that pyrolysis (step 5, example 1, Figure 12) can be used for the isolation of tetramantane.

Prior to pyrolysis, non-diamondoid components (Figure 23A) were present in the tetramantane-containing fraction (distillation hold-up fraction, composition similar to cut 1, Figure 17). Pyrolysis degrades the non-diamondoid components into easily removed gases and coke-like solids. As shown in Figure 23B, the non-diamondoid peaks disappeared after pyrolysis.

Pyrolysis was performed by heating the tetramantane-rich fraction at 450° C. under vacuum in a reactor for 20.4 hours.

Example 5C: Isolation of tetramantane using a single HPLC system

Isolation of diamondoids using HPLC

In addition to the gas chromatographic and pyrolysis methods described above, HPLC was also shown to provide sufficient enrichment of the tetramantanes for their crystallization. Columns suitable for use are known to those skilled in the art. In some cases, reverse phase HPLC with acetone as the mobile phase can be used to perform this purification. A preparative HPLC experiment was performed on feed A, gas condensate, distillate fractions corresponding to cut #1 at the cut point (Figure 17) and the HPLC chromatogram was recorded. Nine fractions were taken in this experiment. The HPLC columns used were two 25 cm x 10 mm I.D. Vydac octadecylsilane 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 tetramantane-containing fraction having a concentration of 55 mg/mL was injected into the column. The column was assembled by using acetone at 2.00ml/min as the mobile phase carrier.

Figure 24 (A, B) compares the gas chromatograms of the starting material (Figure 24A) and HPLC fraction #6. HPLC fraction #6 was substantially enriched in tetramantane, Figure 24B versus starting material (Figure 24B versus starting material (Figure 24A)). Tetramantane #2 in HPLC fraction #6 was close to a concentration sufficient to cause its crystallization.

Example 5D: Isolation of individual tetramantane isomers by HPLC using multiple columns with different selectivities

As shown in Example 5C, tetramantane can be isolated using the HPLC method. In this example, HPLC columns of different selectivities were used to isolate the individual tetramantane isomers. Figure 25 shows the preparative separation of tetramantane using an octadecylsilane (ODS) HPLC column with acetone as the mobile phase. The distillation product used as starting material in Example 5B was the starting material. Specifically, a preparative HPLC fractionation of the retentate fraction from the atmospheric distillation of Feed B conducted at about 650°F was performed. The first column consists of two Whatman M2010/50 (x2) ODS columns operated in series, using 5.00ml/min acetone as the mobile phase (590psi), the 0.500ml infusion contains a retentate concentration of 56mg/ml in acetone fraction. The obtained chromatogram is shown in FIG. 25 . Tetramantane #1 eluted first on the HPLC system, tetramantane #3 eluted second and tetramantane #2 eluted last (Figure 25). The detector used is a differential refractometer. From this experiment, fraction 12 (Figure 25) was taken for further purification.

Further purification of fraction 12 can be achieved by using a Hypercarb-S HPLC column of different specificity than the above ODS column in order to isolate tetramantane #2 (Figure 26). Two Hypercarb-S columns (manufactured by Thermo Hypersil, Penn, USA), 4.6mm I.D. × 250mm, operated in series, using 1.00mL/min of acetone as the mobile phase (180psi), in acetone concentration of 4mg/ml of 50 For microliter injections, also use a differential refractometer. Tetramantane #3 elutes first on this Hypercarb HPLC system, tetramantane #1 elutes second and tetramantane #2 elutes last (Figure 14). Tetramantane #2 was fractionated from this HPLC experiment (Figure 26) and its purity is shown in Figures 28A and B. Hypercarb HPLC experiments on ODS HPLC cutoffs resulted in the isolation of all tetramantanes (enantiomers can be separated by chiral HPLC methods).

Figure 27A shows the GC/MS total ion chromatogram (TIC) of the HPLC fraction containing tetramantane #1; and below that figure, Figure 27B shows its mass spectrum. Figure 29A shows the GC/MS total ion chromatogram (TIC) of the HPLC fraction containing isolated tetramantane #3; and Figure 29B below shows the mass spectrum.

Example 5E: Isolation of Substituted Tetramantane

Alkyl tetramantanes can be purified using the methods described for non-alkylated tetramantanes given in Examples 5A to 5D. Figure 30 shows the isolated monomethylated tetramantane having a molecular weight of 306, giving a mass spectral molecular ion of m/z 306, and showing the mass spectral loss of the methyl group, giving a mass spectral fragment ion of m/z 291 (tetramantane indication of the alkane moiety). This alkylated compound was isolated by Hypercarb HPLC and showed a retention time of 11.46 minutes in our GC/MS system (Figure 30). An additional HPLC separation or preparative GC (as in Examples 3 and 4) was necessary to isolate some of the alkyltetramantanes.

Example 6A: Isolation of Pentamantane by Preparative Gas Chromatography

Steps 1-4 of Example 1 were repeated (FIG. 12). In Step 5, 5.2 g of feedstock B 650°F + residue cut 5 (Table 3, Figure 18) was pyrolyzed at 450°C under vacuum for 16.7 hours. This product was worked up according to step 6 of Example 1.

The eluate from column chromatography (step 6) was analyzed by GC/MS to determine the GC retention times of the pentamantane isomers. The individual pentamantane components with a molecular weight of 344 are numbered according to their elution order in the GC/MS analysis.

A two-column preparative capillary gas chromatograph was then used to isolate pentamantane from the product of step 6 above. Results for exemplary properties of pentamantane #1 are shown in FIG. 31 . The GC peak containing pentamantane #1 on the first column is designated as the "peak intercepted and sent to column 2" in Figure 31A.

The first column is used to concentrate the pentamantane by taking cuts and then passing to the second column. A second column, phenyl-methylsiloxane, DB-17 equivalent, further separated pentamantane #1 from the other species. Material in the desired peak designated "Sent to Collector" was sent to GC Collector Fraction 6 where crystals of pentamantane #1 would accumulate (see Figure 3 IB). GC/MS analysis of the collector #6 material (Figure 32) showed it to be pentamantane (in the pentamantane reference GC/MS retention time system setting of this preparative GC program), the first eluting pentamantane Alkane (#1) showed a retention time of 16.233 min. Figures 32A and B show high purity pentamantane #1 exiting GC collector 6. This procedure can be repeated to isolate four other pentamantanes and three enantiomeric pairs, which can be separated using chiral HPLC or other resolution techniques.

Highly concentrated pentamantane is crystallized directly in the collector or crystallized from solution. Under a microscope at 3OX magnification, crystals of pentamantane #1 could be seen in the preparative GC collector 6 (see Figure 33A). These crystals are clear and exhibit a high refractive index. Crystals of pentamantane #1 never existed prior to this isolation. Further concentration by preparative GC is required when the concentration is not high enough for crystallization to occur. Figure 33B is a photomicrograph of two pentamantanes co-crystallized in a preparative GC collector.

After obtaining crystals of suitable size, the non-enantiomeric pentamantane material was sent for structure determination by X-ray diffraction. Enantiomeric pentamantanes can be further separated to resolve their two components.

Example 6B: Isolation of Pentamantane by HPLC

Steps 1-6 of Example 6A were repeated. The GC/MS analysis reference numbers and retention times for 344 molecular weight pentamantane were as follows:

Pentamantane reference number# 1 2 3 4 5 6 GC/MS(min.) retention time ^* 13.68 15.26 15.31 15.72 15.85 16.06

^* (HP-5MS, 0.25 micron membrane, 0.25mm ID×30m, helium carrier gas)

The ODS HPLC fraction containing pentamantane #1 given in Figure 34 was further purified by using Hypercarb HPLC (Figure 35) to isolate pentamantane #1. Figure 14 shows how ODS HPLC and Hypercarb HPLC were used together to isolate the remaining pentamantane. ODS and Hypercarb columns can also be used in reverse order for these isolations. Figure 36 shows the GC/MS total ion chromatogram (TIC) of isolated pentamantane #1. The lower half of Figure 36 presents the mass spectrum of the pentamantane #1 GC/MS peak. As shown in Figures 14 and 34, various remaining ODS HPLC fractions contained other pentamantanes. By using a method similar to the above, i.e. using Hypercarb (as shown in Figure 14) or another suitable column to fractionate the ODS fraction containing pentamantane and collect at corresponding elution times, resulting in remaining pentamantane in the form of High purity isolation occurs as shown in Figures 37-41. Specifically, Figure 37 illustrates the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #2 isolated using two different HPLC columns; Figure 38 illustrates pentamantane #2 isolated using two different HPLC columns. GC/MS total ion chromatogram (TIC) and mass spectrum of adamantane #3; Figure 39 illustrates the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #4 isolated using two different HPLC columns; Figure 40 illustrates the GC/MS total ion chromatogram (TIC) and mass spectrum of pentamantane #5 isolated using two different HPLC columns; and Figure 41 illustrates the pentamantane #5 isolated using two different HPLC columns. 6 GC/MS total ion chromatogram (TIC) and mass spectrum. The enantiomeric pentamantanes were not resolved in GS/MS, therefore, these enantiomeric pairs are numbered with single numbers. These enantiomers can be separated by chiral separation methods. Additionally, as previously indicated, there is a condensation isomer of pentamantane having a molecular weight of 330, which is more sterically strained and occurs in considerably lower concentrations. This pentamantane component has been observed in the GC/MS analysis of the pyrolysis product of Fraction 5 purified using step 6 of Example 1 (Figure 12). This pentamantane component elutes at 14.4 minutes in the analysis of Example 1, Step 4, and was isolated using the procedure in that Example.

Embodiment 6C: the purification of substituted pentamantane

Substituted pentamantanes are present in starting materials A and B. Substituted pentamantanes can be enriched from these feedstocks and purified using the methods described for non-alkylated pentamantanes in Examples 1-4. The enriched monomethylated pentamantane in this case had a molecular weight of 358 (mass spectral molecular ion at m/z 358 was obtained and showed mass spectral loss of the methyl group, giving m/z 343 mass spectral fragment ion ( indication of the pentamantane moiety)). This alkylated compound was enriched in ODS HPLC fraction #31 and was further purified to form crystals by an additional HPLC separation method, or by a preparative GC procedure (as in Example 3).

Example 7A: Isolation of the hexamantane component

The purpose of this example is to illustrate the procedures that can be used for the enrichment and separation of the thirty-nine hexamantane components. The procedure of Example 1 was repeated with the following changes. In Step 5, 34.4 g of Feedstock B 650°F residue fraction #6 (Table 3, Figure 18) was pyrolyzed at 450°C under vacuum for 17.3 hours.

The eluate from column chromatography (step 6) was analyzed by GC/MS to determine the GC retention time of hexamantane. The individual hexamantane components with a molecular weight of 396 are numbered according to their elution order in the GC/MS analysis. These hexamantanes are the most abundant and convenient choices. Similar analyzes can be done for other molecular weights. Hexamantane elution times were between 17.88 minutes (hexamantane #1) and 19.51 minutes (hexamantane #7) in this GC/MS analysis. Retention times will vary with changing GC columns and conditions that require re-measurement of retention times. Figure 13A presents another GC/MS analysis of the hexamantane component.

A two-column preparative capillary gas chromatograph was then used to isolate the hexamantanes from the distillate fraction purified by column chromatography. The hexamantane cut-off time was set for the first preparative capillary GC column, methylsiloxane DB-1 equivalent, by using the retention time and the model from the GC/MS analysis. The results are shown in Figure 42A and were identified as the "Peak Intercepted and Sent to Column 2", which contained two of the hexamantane components.

The first column was used to concentrate the hexamantanes by taking cuts before passing to the second column (see Figure 42 for illustrations of hexamantanes #2 and #8). A second column, phenyl-methylsiloxane DB-17 equiv., was used to further isolate and purify the hexamantanes before isolating the desired peaks and retaining them in each collector (collectors 1-6). GC collector fraction 1 was collected and further processed to isolate hexamantane #2. GC collector fraction 3 was collected and further processed to isolate hexamantane #8. Subsequent GC/MS analysis of collector #1 material (Figure 43) showed it to be hexamantane #2, based on GC/MS analysis from an earlier run. Similarly, GC analysis of collector #3 material (Figure 44) showed it to be primarily hexamantane #8. This procedure was repeated to isolate other hexamantanes.

The highly concentrated hexamantane is then crystallized directly in the collector or from solution. Under a microscope at 3OX magnification, crystals were visible in the preparative GC collector fraction 1 (see Figure 45). These crystals are clear and exhibit a high refractive index. Crystals of hexamantane #2 never existed prior to this isolation. Further concentration by preparative GC is required when the concentration is not high enough for crystallization to occur. 46 is a photomicrograph of hexamantane #8 crystallized in preparative GC collector 3. Crystals of hexamantane #8 never existed prior to this isolation.

After obtaining crystals of suitable size, the diastereoisomeric hexamantane fraction was sent for structure determination by X-ray diffraction. The enantiomer hexamantane must be further separated to resolve the two components.

Example 7B: Isolation of hexamantane using a single HPLC system.

The HPLC columns used were two 50 cm x 20 mm I.D. Whatman octadecylsilane (ODS) columns operated in series (Whatman columns are manufactured by Whatman Inc., USA). A 500 microliter sample of a solution of the pyrolysis product saturated hydrocarbon fraction (54 mg) of Cut 6, the product of step 6 of Example 1, was injected into the columns. The columns were assembled using acetone at 5.00 ml/min as the mobile phase carrier. Some of the HPLC fractions reached the required purity for each hexamantane to crystallize, such as for hexamantane #8 in ODS HPLC fraction #39 (Figure 47), hexamantane in ODS HPLC fraction #48 Adamantane #10 (FIG. 48) and hexamantane #6 (FIG. 49) in ODS HPLC fraction #63. Alternatively, a Hypercarb column (manufactured by Thermo Hypersil, Penn, USA) or other suitable column can be used to purify the hexamantanes to the concentration required to allow their crystallization to occur. A preparative Hypercarb HPLC experiment of feedstock B Fraction 6 pyrolysis product saturate fraction was performed and a differential refractometer was used to record the HPLC chromatograms. Fractions (eg, Figure 50) were drawn during use and showed that most of the hexamantanes showed different elution times from one another on the Hypercarb HPLC system (checked by GC/MS analysis) (Figure 20).

Example 7C: Isolation of hexamantane using multiple HPLC columns with different selectivities

Hypercarb HPLC fractions were used to obtain the high purity hexamantane #13 shown in Figure 51. Additional ODS HPLC fractions and Hypercarb HPLC cuts can be used to isolate the remaining hexamantane. ODS and Hypercarb columns can also be used in reverse order for these isolations. Figure 52 shows the GC/MS total ion chromatogram (TIC) of the Hypercarb HPLC fraction containing hexamantane #7. The lower half of Figure 52 presents a mass spectrum of GC/MS peaks showing isolated hexamantane #7 in high purity.

Various remaining ODS HPLC fractions (Figure 19) containing other hexamantanes could be separated in the same manner. Using a method similar to the above, ie utilizing a Hypercarb or other suitable column to fractionate the hexamantane-containing ODS fraction and collect at corresponding elution times, can result in the isolation of the remaining hexamantane in high purity. This is also true for the hexamantane of molecular weight 382, the "irregular" hexamantane, which is much less abundant in our feedstock than the hexamantane exhibiting a molecular weight of 396. Figures 53 and 54 show the reconstructed ion chromatograms showing m/z 382 of hexamantane occurring at 18.30 min. and 18.07 min., respectively. Figures 53 and 54 also show the corresponding mass spectra for these 18.30 min. and 18.07 min. peaks, indicating the presence of 382 molecular weight hexamantane in the saturate fraction in the product from the pyrolysis process of feedstock B distillation fraction #6. The 382 molecular weight hexamantane exhibits internal bond strain, lower stability and correspondingly lower concentration than the 396 molecular weight hexamantane, making the 382 molecular weight hexamantane a less preferred hexamantane.

The enantiomer hexamantane was not resolved in GS/MS, therefore, these enantiomeric pairs are numbered with single numbers. These enantiomers can be isolated by chiral separation methods.

Example 7D: Isolation of Substituted Hexamantanes

Substituted hexamantanes including alkylhexamantanes were also present in Feedstocks A and B. These natural substituted hexamantanes have similar utility to the unsubstituted hexamantanes, can be used as useful intermediates in various hexamantane applications (e.g. polymer production) and can be dealkylated to give the corresponding unsubstituted hexamantanes. Derivatized hexamantane. Therefore, a method for isolating each substituted hexamantane was devised and exemplified by the isolation of the alkyl substituted component. Substituted hexamantanes, including aminohexamantanes, can be isolated in high purity by a single HPLC separation using appropriate distillation cuts, as exemplified by FIG. 55 . Figure 55 shows that fraction #55 from the ODS HPLC separation run of Feedstock B, the saturate fraction in the pyrolysis of Distillation Fraction 6, contained methylated hexamantane at high purity. Monomethylated hexamantane had a molecular weight of 410 (mass spectral molecular ion at m/z 410 was obtained and showed mass spectral loss of the methyl group, giving m/z 395 mass spectral fragment ions (Figure 55B)). Isolation of substituted hexamantane components by HPLC may require multiple columns with different selectivities. For example, ODS and Hypercarb HPLC columns were run sequentially to isolate the methylcyclohexamantane component (methyl substituted hexamantane with a molecular weight of 342) from the distillation cut 6-pyrolysis product saturate fraction. From the first ODS HPLC experiment, fractions #23-26 were pooled and removed for further purification on a second HPLC system. This pooled fraction (Figure 56) contains hexamantane (molecular weight 342, called cyclohexamantane) eluting at 12.31 minutes on our GC/MS system, and A mixture of three methylcyclohexamantanes, appearing at minutes. Further purification of this mixture (ie pooled ODS HPLC fractions #23-26) was achieved by using a Hypercarb stationary phase HPLC column. A 50 microliter sample of approximately 1 mg of this pooled fraction in acetone was injected onto a Hypercarb column operated with a differential refractive index detector, 10 mm I.D. x 250 mm using acetone at a flow rate of 3.00 mL/min as mobile phase (480 psi) middle. In this Hypercarb system methylcyclohexamantane #1 elutes predominantly in fractions 18-22 and methylcyclohexamantane #2 predominantly elutes in fractions 23-25. Methylcyclohexamantanes #1 and #2 were isolated in sufficient purity to form crystals. The GC/MS total ion chromatograms and mass spectra of these compounds are given in Figures 57 and 59 and shown as crystals in the photomicrographs in Figures 59 and 60. Figure 59 illustrates methylcyclohexamantane crystals precipitated from Hypercarb HPLC fractions #19-21 and Figure 60 illustrates methylcyclohexamantane crystals precipitated from Hypercarb HPLC fraction #23.

Enantiomeric pairs must be further separated to resolve the bicomponents. After obtaining crystals of suitable size, the diastereoisomeric alkylhexamantanes were sent for structure determination by X-ray crystallography.

Example 8A: Isolation of Heptamantane Components

The eluate from column chromatography (step 6, Figure 12) was analyzed by GC/MS to determine the GC retention time of heptamantane. The individual heptamantane components with molecular weights of 394 and 448 are numbered according to their elution order on our GC/MS analysis (see Figure 13A for representative analytical values). Molecular weight 448 heptamantane, the most abundant heptamantane family, was chosen for convenience in this example. Similar analyzes can be done for other molecular weight heptamantanes.

A two-column preparative capillary gas chromatograph was then used to isolate heptamantanes from the distillate fraction purified by column chromatography. Set the heptamantane cutoff for the first preparative capillary GC column, methylsiloxane DB-1 equivalent, by using the retention time and model from the GC/MS analysis (from step 2 above, Figure 12) time. Results of an exemplary nature are shown at the top of FIG. 61 , designated as "Peaks Intercepted and Sent to Column 2," which contained two of the heptamantanes from Feedstock B.

The first column was used to concentrate the heptamantanes by taking individual cuts before feeding to the second column (see Figure 61 for illustration of heptamantane #1 and #2). A second column, phenyl-methylsiloxane, DB-17 equivalent, was used to further separate and purify the heptamantane component, which was then used to isolate the desired peaks and retain them in each vial (vial 1 -6). GC collector fraction 2 was collected and further processed to isolate heptamantane #1. GC collector fraction 4 was collected and further processed to isolate heptamantane #2. Subsequent GC/MS analysis of collector #2 material (FIG. 62) showed it to be heptamantane #1, based on GC/MS analysis of an earlier run of step 4. Similarly, GC analysis of collector #4 material (FIG. 63) showed it to be heptamantane #2. This procedure was repeated to isolate the other heptamantane components.

The highly concentrated heptamantane is then crystallized directly in the collector or from solution. Under a microscope at 3OX magnification, crystals were visible in the preparative GC collector fraction 2 (see Figure 64). These crystals are clear and exhibit a high refractive index. Crystals of heptamantane component #1 never existed prior to this isolation. Further concentration by preparative GC is required when the concentration is not high enough for crystallization to occur. 65 is a photomicrograph of heptamantane fraction #2 crystallized in preparative GC collector 4. Crystals of heptamantane component #2 never existed prior to this isolation.

After obtaining crystals of suitable size, the heptamantane material was sent for structure determination by X-ray diffraction. The enantiomer heptamantanes can be further separated to resolve their two components.

Example 8B: Purification of a single heptamantane isomer

HPLC also showed sufficient enrichment of some heptamantanes to crystallize them.

The HPLC columns used were the same as those given in the other examples (ODS and Hypercarb). A 500 microliter sample of a solution of the cut 7 pyrolysis product saturated hydrocarbon fraction (product of step 6, Figure 12) was injected into the ODS column. The pyrolysis of cut 7 used 25.8 g and heated at 450 °C for 16 hours. Some of the ODS HPLC fractions reached the purity required for crystallization of the individual heptamantanes, as shown for heptamantane #1 in ODS HPLC fraction #45 (Figure 66). Others, such as heptamantane #2 in ODS HPLC fraction #41 (Figure 67), heptamantane #9 in ODS HPLC fraction #61 (Figure 68), and in ODS HPLC fraction #87 ( Heptamantane #10 in Figure 69) required further purification on HPLC systems with different selectivities. The ODS fraction (FIG. 13B) was run on the Hypercarb column to achieve the required purity for the crystallization of the individual heptamantane fractions, as for the heptamantane fraction #1 and the heptamantane fraction in Hypercarb HPLC fraction #55 alkane #2 (Figure 71) as shown. The higher diamondoids in the various HPLC fractions can be separated using other chromatographic techniques, including preparative gas chromatography, and additional HPLC experiments using columns with different selectivities (described below). Alternatively other techniques known in the art of crystallization can be used, including but not limited to fractional sublimation, stepwise recrystallization or zone refining for the purification of heptamantane.

Isolation of the remaining heptamantane can be caused by using a method similar to above, ie using a Hypercarb or other suitable column to fractionate the heptamantane-containing ODS fraction and collect at corresponding elution times. This is also true for the heptamantanes with molecular weights of 420 and 434, which are much less abundant in our feedstock than the heptamantane components exhibiting molecular weights of 394 and 448. The heptamantane component with a molecular weight of 420 was revealed in ODS HPLC fraction #61 (Figure 73A), with a very strong molecular ion in the mass spectrum for the m/z 420 component that appeared at 16.71 min (in this case m/z 420, Figure 73B). The mass spectrum, with its low number and abundance of prominent molecular ions and fragments, is characteristic of the diamondoid component.

Example 8C: Isolation of Substituted Heptamantanes

Substituted heptamantanes including alkyl heptamantanes were also present in feedstocks A and B. Alkyl heptamantanes can be purified by removing non-diamondoid impurities from the feedstock using pyrolysis as described above. Certain alkyl heptamantanes survived the pyrolysis process, as did the previously identified heptamantane components. Substituted heptamantanes, including alkyl heptamantanes, can be isolated in high purity using a single HPLC separation illustrated by FIG. 74 . Monomethylated heptamantane has a molecular weight of 408 (mass molecular ion obtained at m/z 408 and shows mass spectral loss of the methyl group and mass spectral fragment ion at m/z 393 (indicative of the heptamantane moiety) (FIG. 74B)).

Example 9A: Isolation of octamantane components

The octamantane-enriched fraction from step 6 was subjected to reverse phase HPLC. In some cases, reverse phase HPLC with acetone as the mobile phase can be used to perform this purification. A preparative ODS HPLC experiment of feedstock B distillation cut 7 pyrolysis product saturate fraction (used in Example 8A) was performed and a differential refractometer was used to record the HPLC chromatograms. HPLC fractions were analyzed by GC/MS to determine octamantane HPLC elution time and monitor purity (see Figure 13A for representative analytical values). The HPLC column used was the same ODS and Hypercarb system used in the previous examples. A 500 microliter sample of the acetone solution of the pyrolysis product saturated hydrocarbon fraction (25 mg) of Cut 7 was injected into the ODS column. By using this HPLC system, some of the octamantanes achieved the purity required to crystallize the individual octamantanes. For example, Figure 75 illustrates the GC/MS total ion chromatogram and mass spectrum of the HPLC fraction in which Octamantane #1 had been purified to the extent that it could form crystals (see Figure 76). HPLC fraction 63 yielded both octamantane #3 and #5 (Figure 77), which co-crystallized from this fraction (Figure 78).

For high purity isolation of other octamantane components (eg, Figures 79 and 80), multiple columns can be used, eg Hypercarb.

Example 9B: Isolation of Substituted Octamantane Components

Alkyl octamantanes can be purified using the methods described for the non-alkylated octamantanes given in Examples 1 and 3. Figure 81 (A/B) shows that ODS HPLC fraction 94 contains methylated octamantane in high purity. Monomethylated octamantane has a molecular weight of 460 (mass spectral molecular ion at m/z 460 is obtained and shows mass spectral loss of the methyl group, mass spectral fragment ion at m/z 445 is obtained (indicative of the octamantane moiety) (FIG. 81B)). Likewise, when more than one alkyl octamantane is present in the ODS or Hypercarb HPLC fraction, additional HPLC separation of this fraction or a preparative GC procedure (as in Example 3) can yield highly pure alkyl octamantane Octamantane.

Example 10A: Isolation of nonamantane components

A preparative ODS HPLC experiment of feedstock B distillation cut 7 pyrolysis product saturated hydrocarbon fraction (raw material described in Example 8A) was performed, and the HPLC fraction was analyzed by GC/MS to determine the nonamantane HPLC elution time ( Figure 82) and monitor purity. A 500 microliter sample of the acetone solution of the pyrolysis product saturated hydrocarbon fraction (25 mg) of Fraction 7 was injected into the column. The column was assembled by using acetone at 5.00ml/min as the mobile phase carrier.

For the isolation of the nonamantane component in high purity, multiple HPLC columns can be used. To illustrate this method, HPLC columns ODS and Hypercarb (as described in previous examples) with different selectivities were sequentially used to isolate a single nonamantane. From the ODS HPLC experiments, nonamantane-containing fractions 84-88 were pooled and further purified on a Hypercarb HPLC system.

We injected approximately 1 mg of a 50 microliter sample of ODS HPLC pooled fractions (84-88) in dichloromethane onto two Hypercarb columns operating in series, two 4.6mmI.D. x 200mm, using dichloromethane Use 1.30mL/min as the mobile phase.

Figure 83 shows the GC/MS total ion chromatogram (TIC) of the Hypercarb HPLC fraction containing concentrated nonamantane. The lower half of Figure 83 presents the mass spectrum of the GC/MS peaks. Nonamantane was isolated by a third run of HPLC experiments using the same Hypercarb stationary phase column, but with a solvent consisting of dichloromethane/acetone (70:30 volume percent, operating at 1.00 mL/min). The obtained isolated nonamantane crystals and the corresponding mass spectrum are shown in FIG. 84 .

By using a method similar to the above, that is, using columns with different selectivities, such as Hypercarb or other suitable columns, to fractionate the ODS HPLC fraction containing nonamantane, we isolated nonamantane with a molecular weight of 498 in high purity. This method was able to be repeated to isolate nonamantane of molecular weight 552, as well as nonamantanes of molecular weight 538, 484 and 444, which were in lower abundance in our feedstock, respectively. It should be noted that the enantiomer nonamantane was not resolved in GS/MS, however these enantiomers could be isolated by chiral separation methods.

Example 10B: Isolation of Substituted Nonamantanes

Substituted nonamantanes were also present in starting materials A and B. Alkyl nonamantanes can be purified using the methods described for non-alkylated nonamantanes. Figure 85 (A/B) shows methylated nonamantane in the pyrolysis product of distillate fraction #7. One type of monomethylated nonamantane has a molecular weight of 512 (mass spectral molecular ion of m/z 512 was obtained and showed mass spectral loss of the methyl group, mass spectral fragment ion of m/z 497 was obtained (nonamantane structure Partial indication) (Fig. 85B)). Where more than one type of alkylnonamantane is present, these can be isolated by using ODS or Hypercarb columns, additional HPLC separation, or by preparative GC to obtain alkylnonamantanes of high purity.

Example 11A: Isolation of Decadamantane Components

A preparative ODS HPLC experiment of feedstock B distillation cut 7 pyrolysis product saturate fraction was performed, and the HPLC fraction was analyzed by GC/MS to determine the decamantane HPLC elution time (Figure 86) and monitor the purity. The HPLC columns used were two 50 cm x 20 mm I.D. Whatman octadecylsilane (ODS) columns operated in series. A 500 microliter sample of the acetone solution of the pyrolysis product saturated hydrocarbon fraction (25 mg) of Fraction 7 was injected into the column. The column was assembled by using acetone at 5.00ml/min as the mobile phase carrier.

For the isolation of the decamantane component in high purity, multiple HPLC columns can be used. To illustrate this method, HPLC columns with different selectivities were sequentially used to isolate a single decamantane. The first HPLC system consisted of the same ODS column as previously described. From this HPLC experiment, decamantane-containing fractions 74-83 were combined and further purified on a second HPLC system. Five such experiments were performed and all decamantane-containing fractions from these experiments were pooled. This combined fraction contained decamantane with a molecular weight of 456 and various impurities.

To purify the pooled HPLC fractions 74-83 from the ODS HPLC separation, we injected a 50 μl sample of approximately 1 mg of the ODS HPLC pooled fraction in acetone/dichloromethane (70:30 volume percent) into the tandem operation On two Hypercarb columns, two 4.6mm I.D.×200mm, using acetone/dichloromethane (70:30 volume percent) at 1.00mL/min as mobile phase (480psi).

Figure 87 shows the GC/MS total ion chromatogram (TIC) of the Hypercarb HPLC fraction containing concentrated decamantane eluting at 18.55 minutes. The lower half of Figure 87 shows the mass spectrum of the GC/MS peaks, with the main peak at m/z 456. The obtained [1231241(2)3] decamantane crystals with a molecular weight of 456 and the mass spectrum are shown in FIG. 88 . 456 decamantane eluted on the Hypercarb HPLC system before pentamantane #3 due to its dense, low surface area structure (Figure 10). This property of 456 molecular weight decamantane makes it possible to isolate it in high purity.

By using a method similar to the above, that is, using columns with different selectivities, such as Hypercarb or other suitable columns, to fractionate the ODS HPLC fraction containing decamantane, we isolated decamantane with a molecular weight of 456 in high purity. This method can be repeated to isolate decamantane having a molecular weight of 496 (shown in Figure 89, in the saturated fraction of the pyrolysis product of distillate fraction #7) and molecular weight 550 or 604, and molecular weight 536 , 576 and 590 decamantanes, which are in lower abundance in our feedstock, respectively. It should be noted that the enantiomer decamantane was not resolved in GS/MS, however these enantiomers could be isolated by chiral separation methods.

Example 10B: Isolation of Substituted Decamantanes

Substituted decamantanes were also present in starting materials A and B. Alkyl decamantanes can be purified using the methods described for non-alkylated decamantanes. Figure 90 shows that the saturated fraction of pyrolysis products of Distillate Fraction #7 contained methylated decamantane. One type of monomethylated decamantane has a molecular weight of 470 (giving a mass spectral molecular ion of m/z 470). Likewise, when more than one alkyldecamantane is present in an ODS or Hypercarb HPLC fraction, secondary HPLC separation of this fraction or an alternative preparative GC procedure can yield alkyldecamantanes of high purity.

Example 12: Isolation of Undecamantane Components

For the isolation of the undecadamantane component in high purity, multiple HPLC columns can be used. This method demonstrates the isolation of a single decamantane using successive HPLC columns with different selectivities using decamantane (Example 11). A suitable starting material, Feedstock B, pyrolysis product of distillation cut 7 was shown to contain undecamantane (Figure 91).

Concentrated undecadamantane from ODS HPLC fraction 100+ (Figure 13B) is shown in Figure 92. This fraction can be purified on a Hypercarb HPLC column using a system (identical to that explained in Example 11) to isolate the undecadamantane. This method can be repeated to isolate undecadamantane of molecular weight 656 and/or 602, and undecadamantane of molecular weight 642, 628, 588, 548 or 534, respectively, which are expected to be less abundant in our feedstock. Spend.

Claims (130)

1. Enriched selected higher diamondoid components, neither including enriched unsubstituted trans-tetramantane nor enriched cyclohexamantane, wherein the enriched all Selected higher diamondoid components exhibit a purity of at least 25 wt%. 2. A composition enriched in one or more selected higher diamondoid components, wherein the one or more selected higher diamondoid components comprise at least 1% by weight of the composition, provided that , when there is only one selected higher diamondoid component, it is neither the unsubstituted trans-tetramantane nor the unsubstituted cyclohexamantane. 3. The composition of claim 2, wherein the one or more selected higher diamondoid components comprise at least 10% by weight of the composition. 4. The composition of claim 2, containing 50-100 wt% of one or more selected higher diamondoid components. 5. The composition of claim 2, containing 70-100 wt% of one or more selected higher diamondoid components. 6. The composition of claim 2, comprising 95-100 wt% of one or more selected higher diamondoid components. 7. The composition of claim 2, comprising 99-100 wt% of one or more selected higher diamondoid components. 8. The composition of claims 2-7, wherein the one or more selected higher diamondoid components is a single selected higher diamondoid component. 9. Compositions comprising diamondoids enriched in one or more selected higher diamondoid components relative to the total amount of diamondoids, wherein at least 25% by weight of the total amount of diamondoids is one or more selected higher diamondoids, provided that, when there is only one selected higher diamondoid component, it is neither unsubstituted trans-tetramantane nor cyclohexa Adamantane. 10. The composition of claim 9, wherein the one or more selected higher diamondoid components are components within a single diamondoid family. 11. The composition of claim 9, wherein the one or more selected higher diamondoid components is a single selected higher diamondoid component. 12. The composition of claims 1-11, wherein the selected higher diamondoid component comprises one or more tetramantane components. 13. The composition of claim 12, wherein the one or more tetramantane components are a single tetramantane component. 14. The composition of claim 13, wherein the single tetramantane component is iso-tetramantane. 15. The composition of claim 13, wherein the single tetramantane component is a twisted-tetramantane. 16. The composition of claim 13, wherein the single tetramantane component is a single enantiomer of twisted-tetramantane. 17. The composition of claim 12, wherein the tetramantane component comprises a substituted tetramantane component. 18. An enriched iso-tetramantane exhibiting a purity of at least 25 wt%. 19. Enriched twisted-tetramantane enantiomer A exhibiting a purity of at least 25 wt%. 20. Enriched twisted-tetramantane enantiomer B exhibiting a purity of at least 25 wt%. 21. The enriched tetramantane of claims 18-20 in crystalline form. 22. The composition of claims 1-11, wherein the selected higher diamondoid component comprises one or more pentamantane components. 23. The composition of claim 22, wherein the one or more pentamantane components are a single pentamantane component. 24. The composition of claim 22, wherein the one or more pentamantane components are isolated optical isomers. 25. The composition of claim 22, wherein the one or more pentamantane components are isomeric pentamantane components. 26. The composition of claim 22, wherein the one or more pentamantane components are non-isomeric pentamantane components represented by the general formula _{C25H30 .} 27. An enriched pentamantane fraction exhibiting a purity of at least 25 wt%. 28. The enriched pentamantane fraction of claim 27 in crystalline form. 29. The enriched pentamantane component of claim 27, wherein the pentamantane component is [1231]pentamantane. 30. The enriched pentamantane component of claim 27, wherein the pentamantane component is [1213] Enantiomer A pentamantane. 31. The enriched pentamantane component of claim 27, wherein the pentamantane component is [1213] Enantiomer B pentamantane. 32. The enriched pentamantane component of claim 27, wherein the pentamantane component is [1234] Enantiomer A pentamantane. 33. The enriched pentamantane component of claim 27, wherein the pentamantane component is [1234] Enantiomer B pentamantane. 34. The enriched pentamantane component of claim 27, wherein the pentamantane component is [12(1)3] Enantiomer A pentamantane. 35. The enriched pentamantane fraction of claim 27, wherein the pentamantane fraction is [12(1)3]Enantiomer B pentamantane. 36. The enriched pentamantane component of claim 27, wherein the pentamantane component is [1212]pentamantane. 37. The enriched pentamantane component of claim 27, wherein the pentamantane component is [1(2,3)4]pentamantane. 38. The enriched pentamantane component of claim 27, wherein the pentamantane component is [12(3)4]pentamantane. 39. The enriched pentamantane component of claim 27, wherein the pentamantane component is an unsubstituted pentamantane component. 40. The enriched pentamantane component of claim 27, wherein the pentamantane component is a substituted pentamantane component. 41. The composition of claims 1-11, wherein the selected higher diamondoid component comprises one or more hexamantane components. 42. The composition of claim 41, wherein the one or more hexamantane components are a single hexamantane component. 43. The composition of claim 41, wherein the one or more hexamantane components are isolated optical isomers. 44. The composition of claim 41, wherein the one or more hexamantane components are isomeric hexamantane components. 45. The composition _of claim 41, wherein the one or more hexamantane components are one or more hexamantane components represented by the general formula _C30H36 . 46. The composition _of claim 41, wherein the one or more hexamantane components are one or more hexamantane components represented by the general formula _C29H34 . 47. _An enriched hexamantane component represented by the general formula _C30H36 or _C29H34 , with and without substitution _, exhibiting a purity of at least 25 wt%. 48. The enriched hexamantane fraction of claim 47 in crystalline form. 49. The enriched hexamantane component of claim 47, represented by _the general formula _C29H36 . 50. The enriched hexamantane component of claim 47, represented by _the general formula _C30H36 . 51. The enriched hexamantane component of claim 50 selected from the group consisting of: [1(2)314] Enantiomer A hexamantane [1(2)314]Enantiomer B hexamantane [12(1)32] Enantiomer A hexamantane [12(1)32]Enantiomer B hexamantane [12(1)34] Enantiomer A hexamantane [12(1)34] Enantiomer B hexamantane [12(1,3)4]hexamantane [12(3)14]Enantiomer A hexamantane [12(3)14] Enantiomer B hexamantane [121(2)3] Enantiomer A hexamantane [121(2)3]Enantiomer B hexamantane [12123] Enantiomer A hexamantane [12123] Enantiomer B hexamantane [12131] Enantiomer A hexamantane [12131] Enantiomer B hexamantane [12134] Enantiomer A hexamantane [12134] Enantiomer B hexamantane [12324] Enantiomer A hexamantane [12324] Enantiomer B hexamantane [12341] Enantiomer A hexamantane [12341] Enantiomer B hexamantane [1(2)3(1)2]hexamantane [12(3)12]hexamantane [121(3)4]hexamantane [12121] Hexamantane [12321] Hexamantane [1(2)3(1)4]Enantiomer A hexamantane [1(2)3(1)4] Enantiomer B hexamantane. 52. The enriched hexamantane component of claim 47, wherein the hexamantane component is an unsubstituted hexamantane component. 53. The enriched hexamantane component of claim 47, wherein the hexamantane component is a substituted hexamantane component. 54. An enriched substituted cyclohexamantane fraction exhibiting a purity of at least 25 wt%. 55. The composition of claims 1-11, wherein the selected higher diamondoid components comprise one or more heptamantane components. 56. The composition of claim 55, wherein the one or more heptamantane components are a single heptamantane component. 57. The composition of claim 55, wherein the one or more heptamantane components are isolated optical isomers. 58. The composition of claim 55, wherein the one or more heptamantane components are isomeric heptamantane components. 59. The composition _of claim 55, wherein the one or more heptamantane components are one or more isomeric heptamantane components represented by the general formula _C30H34 . 60. The composition _of claim 55, wherein the one or more heptamantane components are one or more isomeric heptamantane components represented by the general formula _C32H36 . 61. The composition _of claim 55, wherein the one or more heptamantane components are one or more isomeric heptamantane components represented by the general formula _C33H38 . 62. The composition _of claim 55, wherein the one or more heptamantane components are one or more isomeric heptamantane components represented by the general formula _C34H40 . 63. An enriched heptamantane fraction exhibiting a purity of at least 25 wt%. 64. The enriched heptamantane fraction of claim 63 in crystalline form. 65. The enriched heptamantane fraction of claim 63, wherein the heptamantane fraction has a molecular weight of 394. 66. The enriched heptamantane component of claim 63, wherein the heptamantane component is [121321] heptamantane. 67. The enriched heptamantane component of claim 63, wherein the heptamantane component is [123124]heptamantane. 68. The enriched heptamantane component of claim 63, wherein the heptamantane component is an unsubstituted component. 69. The enriched heptamantane component of claim 63, wherein the heptamantane component is a substituted component. 70. The composition of claims 1-11, wherein the selected higher diamondoid components comprise one or more octamantane components. 71. The composition of claim 70, wherein the one or more octamantane components are a single octamantane component. 72. The composition of claim 70, wherein the one or more octamantane components are isolated optical isomers. 73. The composition of claim 70, wherein the one or more octamantane components are isomeric octamantane components. 74. The composition _of claim 70, wherein the one or more octamantane components are one or more isomeric octamantane components represented by the general formula _C33H36 . 75. The composition of claim 70, wherein the one or more octamantane components are one or more isomeric octamantane _components represented by the general formula _C34H38 . 76. The composition _of claim 70, wherein the one or more octamantane components are one or more isomeric octamantane components represented by the general formula _C36H40 . 77. The composition _of claim 70, wherein the one or more octamantane components are one or more isomeric octamantane components represented by the general formula _C37H42 . 78. The composition _of claim 70, wherein the one or more octamantane components are one or more isomeric octamantane components represented by the general formula _C38H44 . 79. An enriched octamantane fraction exhibiting a purity of at least 25 wt%. 80. The enriched octamantane fraction of claim 79 in crystalline form. 81. The enriched octamantane component of claim 79, wherein the octamantane component is an unsubstituted octamantane component. 82. The enriched octamantane component of claim 79, wherein the octamantane component is a substituted octamantane component. 83. The composition of claims 1-11, wherein the selected higher diamondoid component comprises one or more nonamantane components. 84. The composition of claim 83, wherein the one or more nonamantane components are a single nonamantane component. 85. The composition of claim 83, wherein the one or more nonamantane components are isolated optical isomers. 86. The composition of claim 83, wherein the one or more nonamantane components are isomeric nonamantane components. 87. The composition of claim 83, wherein the one or more nonamantane components are isomeric nonamantane components represented by _the general formula _C34H36 . 88. The composition _of claim 83, wherein the one or more nonamantane components are one or more isomeric nonamantane components represented by the general formula _C37H40 . 89. The composition _of claim 83, wherein the one or more nonamantane components are one or more isomeric nonamantane components represented by the general formula _C38H42 . 90. The composition _of claim 83, wherein the one or more nonamantane components are one or more isomeric nonamantane components represented by the general formula _C40H44 . 91. The composition _of claim 83, wherein the one or more nonamantane components are one or more isomeric nonamantane components represented by the general formula _C41H46 . 92. The composition _of claim 83, wherein the one or more nonamantane components are one or more isomeric nonamantane components represented by the general formula _C42H48 . 93. An enriched nonamantane fraction exhibiting a purity of at least 25 wt%. 94. The enriched nonamantane component of claim 93 in crystalline form. 95. The enriched nonamantane component of claim 93, wherein the nonamantane component is an unsubstituted nonamantane component. 96. The enriched nonamantane component of claim 93, wherein the nonamantane component is a substituted nonamantane component. 97. The composition of claims 1-11, wherein the selected higher diamondoid components comprise one or more decamantane components. 98. The composition of claim 97, wherein the one or more decamantane components are a single decamantane component. 99. The composition of claim 97, wherein the one or more decamantane components are isolated optical isomers. 100. The composition of claim 97, wherein the one or more decamantane components are isomeric decamantane components. 101. The composition _of claim 97, wherein the one or more decamantane components are non-isomeric decamantane components represented by the general formula _C35H36 . 102. The composition _of claim 97, wherein the one or more decamantane components are one or more isomeric decamantane components represented by the general formula _C38H40 . 103. The composition _of claim 97, wherein the one or more decamantane components are one or more isomeric decamantane components represented by the general formula _C41H44 . 104. The composition _of claim 97, wherein the one or more decamantane components are one or more isomeric decamantane components represented by the general formula _C42H46 . 105. The composition _of claim 97, wherein the one or more decamantane components are one or more isomeric decamantane components represented by the general formula _C44H48 . 106. The composition _of claim 97, wherein the one or more decamantane components are one or more isomeric decamantane components represented by the general formula _C45H50 . 107. The composition _of claim 97, wherein the one or more decamantane components are one or more isomeric decamantane components represented by the general formula _C46H52 . 108. An enriched decamantane fraction exhibiting a purity of at least 25 wt%. 109. The enriched decamantane fraction of claim 108, in crystalline form. 110. The enriched decamantane fraction of claim 108, wherein the decamantane fraction is [1231241(2)3]decadamantane. 111. The enriched decamantane component of claim 108, wherein the decamantane component is an unsubstituted decamantane component. 112. The enriched decamantane component of claim 108, wherein the decamantane component is a substituted decamantane component. 113. The composition of claims 1-11, wherein the selected higher diamondoid components comprise one or more undecadamantane components. 114. The composition of claim 113, wherein the one or more undecadamantane components are a single undecadamantane component. 115. The composition of claim 113, wherein the one or more undecadamantane components are isolated optical isomers. 116. The composition of claim 113, wherein the one or more undecadamantane components are isomeric undecadamantane components. 117. The composition _of claim 113, wherein the one or more undecadamantane components are one or more isomeric undecadamantane components represented by the general formula _C39H40 . 118. The composition _of claim 113, wherein the one or more undecadamantane components are one or more isomeric undecadamantane components represented by the general formula _C41H42 . 119. The composition of claim 113, wherein the one or more undecadamantane components are one or more non-isomeric undecadamantane components represented by the general formula _{C42H44 .} 120. The composition _of claim 113, wherein the one or more undecadamantane components are one or more non-isomeric undecadamantane components represented by the general formula _C45H48 . 121. The composition _of claim 113, wherein the one or more undecadamantane components are one or more non-isomeric undecadamantane components represented by the general formula _C46H50 . 122. The composition _of claim 113, wherein the one or more undecadamantane components are one or more non-isomeric undecadamantane components represented by the general formula _C48H52 . 123. The composition _of claim 113, wherein the one or more undecadamantane components are one or more non-isomeric undecadamantane components represented by the general formula _C49H54 . 124. The composition _of claim 113, wherein the one or more undecadamantane components are one or more non-isomeric undecadamantane components represented by the general formula _C50H56 . 125. An enriched undecadamantane fraction exhibiting a purity of at least 25 wt%. 126. The enriched undecadamantane fraction of claim 125, in crystalline form. 127. The enriched undecadamantane component of claim 125, wherein the undecadamantane component is an unsubstituted undecadamantane component. 128. The enriched undecadamantane component of claim 125, wherein the undecadamantane component is a substituted undecadamantane component. 129. A method of recovering a composition enriched in higher diamondoid components, the method comprising: a. selecting a feedstock comprising a recoverable amount of higher diamondoid components; b. Remove a sufficient amount of components having a boiling point lower than the higher diamondoid component of the required lowest boiling point under certain conditions to provide a treated feedstock from which higher diamondoids can be recovered components; and c. recovering higher diamondoid components from the treated feedstock by a separation technique selected from the group consisting of chromatographic techniques, thermal diffusion techniques, zone refining, stepwise recrystallization and particle segregation techniques. 130. A method of recovering a composition enriched in higher diamondoid components, the method comprising: a. Select a feedstock comprising recoverable amounts of the higher diamondoid components selected for recovery, non-diamondoid components and groups having a lower boiling point than the lowest boiling higher diamondoid components selected for recovery point; b. Remove a sufficient amount of components having a boiling point lower than the lowest boiling higher diamondoid component selected for recovery under certain conditions, wherein the recoverable amount of the higher diamondoid group selected for recovery remaining in the processed material; c. thermally treating the feedstock recovered in b) above to pyrolyze at least a sufficient amount of non-diamondoid components therein so that selected higher diamondoid components can be recovered from the pyrolytically treated feedstock, wherein in performing pyrolysis under conditions to provide a process feed that retains recoverable amounts of selected higher diamondoid components; and d. recovering selected higher diamondoid components from the treated feedstock by a separation technique selected from the group consisting of chromatographic techniques, thermal diffusion techniques, zone refining, stepwise recrystallization and particle segregation techniques.

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