Methods of extraction and cleaning of the high-molecular diamond-likes and the compositions containing such diamond-likes

FIELD: chemical industry; diamond-mining industry; methods of cleaning of the high-molecular diamond-likes.

SUBSTANCE: the invention is pertaining to the methods of extraction and cleaning of the high-molecular diamond-likes from the hydrocarbons raw materials. The invention provides, that at first they conduct selection of the initial reactant containing tetramantan and others high-molecular diamond-likes, removal from the reactant the components having the boiling temperature less, than the lowest temperature of boiling of tetramantan, and the thermal treatment of the rest for pyrolysis. The pyrolysis is conducted under the conditions providing preservation of tetramantan and other high-molecular diamond-likes. The composition is enriched with the tetramantan and other high-molecular diamond-likes and contains the tetramantan and pentamantan in amount of 10 mass % and 0.5 mass % accordingly with respect to the other the other diamond-likes. The invention allows to produce the compositions containing the high-molecular diamond-likes from the natural raw materials.

EFFECT: the invention ensures production of the high-molecular diamond-likes from the natural raw materials.

21 cl, 7 tbl, 15 ex, 40 dwg

 

BACKGROUND of INVENTION

This invention relates to new methods of extraction and at least partial purification of high-molecular alasoini components from a source of hydrocarbon raw materials (reagents). In particular, the present invention relates to a method of extraction for obtaining compositions enriched in one or more components of macromolecular Almazov.

The present invention also relates to compositions containing higher levels of one or more high molecular Almazov.

In this application contains links to the following publications and patents identified in the description text with Superscript:

1Fort, Jr., et al.,Adamantane: Consequences of the Diamondoid Structure,Chem. Rev 64:277-300 (1964);

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

3Lin, et al.,Natural Occurrence of Tetramantane (C22H28), Pentamantane (C26H32and Hexamantane (30N36) in a Deep Petroleum Reservoir,Fuel 74, (10): 1512-1521 (1995);

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

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

6Alexander, et al., Purificationof Hydrocarbonaceous Fractions,U.S. Patent No. 4,952,748, issued August 28, 1990;

7Alexander, et al., Removal ofof Diamondoid Compunds from Hydrocarbonaceous Fractions, U.S. Patent No. 4,952,749, issued August 28,1990;

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

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

10Partridge, et al.,ShapeSelectiveProcess for Concentrating Diamondoid-Containing Hydrocarbon Solvents,U.S. Patent No. 5,019,665, issued May 28, 1991;

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

12McKervey, SyntheticApproaches to Large Diamondoid Hydrocarbons,Tetrahedron 36:971-992 (1980);

13Wu, et al.,HighViscosityIndex Lubricant Fluid,U.S. Patent No. 5,306,851, issued April 26, 1994;

14Chung et al., RecentDevelopment in High-Energy Density Liquid Fuels,Energy and Fuels 13, 641-649 (1999);

15Balaban et al., Systematic Classification and Nomenclature of Diamond Hydrocarbons-I, Tetrahedron 34, 3599-3606 (1978).

All the above publications and patents included in the description by reference in full, this implies that this is equivalent to the fact that each of the specified individual publications or patents separately incorporated here by reference in full.

Almatadema are hydrocarbon molecules to form the spatial framework, with a very rigid structure, which are imposed fragments (same structure) of the crystal lattice of the diamond1(Fig. 1). The lowest connection almatadema number is adamantane, which is a molecule with ten carbon atoms is composed of one elementary cell of the crystal structure of diamond. Diamanten contains two elementary cell of the crystal structure of diamond, United along the verge, Tremonton three, tetramantane - four, and so on, Despite the fact that adamantane, diamantane and Tremonton have only one isomer, tetramantane has four different isomers, i.e. there are four different forms, containing four diamond unit cell, which coincide with the crystal lattice of the diamond when they overlap. Two of these isomers are enantiomeric (i.e. mirror images of each other). The number of possible isomers increases rapidly for each more macromolecular compounds almatadema series. Because some high-molecular almasoud alasoini crystal cell can be used more than one face, then the increase in the number of different variants of the ratio of the number of hydrogen atoms to the number of carbon atoms, that is, the degree of compaction, which leads to the increasing diversity of molecular masses for each subsequent family of high-molecular Almazov. In Fig. 30 is a table showing the range of macromolecular Almazov.

In different lattice sites source alasoini can be replaced by alkilani, and the possible existence of ogromna the number of their species, replaced by metelli, atrami, Tanami, trimethylene, cuts, etc. that occur under natural conditions in the original crude oil, along with the original almatadema. Alasoini actually present in every form of petroleum products (oil and natural gas liquids), as well as in extracts derived from source rocks.11The natural concentration of Almazov in oil differs in size by orders of magnitude. For example, the concentration of meterdiameter in crude oil with a relatively low maturity obtained from the Central California plains, USA, is of the order of a few parts per million (ppm). Oil with low maturity, extracted from the Smackover formation Jurassic in the Northern part of the Gulf coast, USA, has a concentration of meterdiameter equal to 20-30 ppm (part per million). Petroleum products deep, for example, the condensate from the reservoir deep subjected to significant cracking in the intense heat, can have a concentration of meterdiameter equal to thousands of ppm.

The presence of high concentrations of Almazov some condensates and other raw materials due to the high thermal resistance of Almazov compared with other components of petroleum products. These alasoini may represent the remains of weathering over time due to geologists the definition of processes and temperature conditions, in which there is thermal cracking of other hydrocarbons or their transformation into pyrobitumen emitting gas. Due to the presence of this natural mechanism of enrichment in some condensates alasoini can become the dominant component. In addition, since alasoini are extremely stable molecules, they remain, and their concentration in certain flows of oil products after processing, such as cracking, hydrocracking, etc. In the art adamantane, diamantane, Tremonton and their substituted analogues referred to as "low-molecular almatadema". Tetramantane and more high alasoini and their substituted analogues referred to as "high-molecular almatadema". This nomenclature is used in this description. Low-molecular alasoini components do not have isomers or chirality and can be easily synthesized, which distinguishes them from the "high-molecular Almazov".

As for other properties, alasoini have much more thermodynamically stable structure of all possible hydrocarbons having the same molecular formula, because alasoini have the same internal structure of the crystal lattice, like diamonds. It is well known that diamonds have an extremely high tensile strength extremely low chemical activity, high specific electrical resistance greater than the electrical resistivity of aluminum trioxide (Al2About3), and excellent conductivity.

In addition, molecules tetramantane and other high-molecular Almazov have a size in the nanometer range, and the authors of the present invention believe that, given the presence of the above properties, such compounds would be useful for applications in microelectronics, molecular electronics and nanotechnology. In particular, the rigidity, strength, stability, conductivity, presence of many structural forms and many centers joining in molecules of high molecular weight Almazov make possible the creation of a reliable, durable and high precision devices with nanometer dimensions. According to estimates, microelectromechanical systems (MEMS) (MEMS), made of diamond, should have a service life of 10,000 times greater than the currently applied MEMS of polycrystalline silicon, and diamond is chemically not dangerous and not promotiom allergic reactions when using these systems in Biomedicine.6High alasoini should have similar attractive properties. In addition, some of the numerous isomers of macromolecular Almazov possess chirality, h is o provides the ability to create objects in the field of nanotechnology, possessing high structural specificity and have useful optical properties. The field of application of such high-molecular Almazov include molecular electronics, Photonics, mechanical devices of nanometer size, polymers with nanometer structure and other materials.

Despite the advantages of tetramantane and other high-molecular Almazov, the prior art does not provide compositions containing these high alasoini.

For example, Lin, et al.3reported the presence in nature of tetramantane, pansamantala and exemestane contained in the oil reservoir deep. However, the authors were able to establish experimentally only the presence of these compounds in the ionized form at mass spectrometric analysis.

Similarly, although the patent Chen, et al.4reveals how the selection of fractions and low molecular weight components Almazov a high degree of purity, in the disclosed methods provided by the distillation of the source reagent containing alasoini 5 top components. These top components contain unsubstituted adamantane substituted adamantane, an unsubstituted diamantane, substituted Diamanten and the unsubstituted Tremonton. In addition, Chen, et al. note that the material in the vessel, the extracted after the above process, the PE Agency, contains a large number of substituted Tramuntana and a small number of tetramantane and pansamantala. However, there have not been disclosed to the relative number of experimentally identified tetramantane and pansamantala in the material in the vessel, and in Table 3 of this reference indicated only the presence of Tramontana and tetramantane in the material in the vessel and not reported attempts to highlight any high molecular Almazov.

Other attempts to retrieve alasoini fractions of natural hydrocarbons is treated to extract low molecular weight Almazov, such as adamantane, diamantane and Tramontana and their analogs containing various side chains, mainly to extract these components from the natural gas stream to prevent the occurrence of operational problems with the extraction of natural gas, due to the deposition of these components in industrial equipment. See, for example, four related patent Alexander, et al.5-8. In one or more of these patents disclosed the following: 1) operation of extraction of low molecular weight Almazov from the gas stream by solvent and additional extraction method sorption on silica gel, 2) operation of extraction of low molecular weight Almazov via a heat exchanger and 3) OPE the situation extraction of low molecular weight Almazov from the gas stream using porous solids, for example zeolite. Removing low molecular weight Almazov from the gas stream is also disclosed in patent Swanson9and removing low molecular weight Almazov of fluid flow are disclosed in patent Partridge, et al.10

Despite the fact that have been established ways of synthesis of Almazov providing all low-molecular Almazov (from adamantane to Tramuntana), by providing supercyclone equilibrium by cations of carbon with controlled thermodynamics of the process, the application of these methods of synthesis for the synthesis of tetramantane and other high-molecular Almazov impossible due to the presence of serious limitations, due to the kinetics (movement) of the reaction. All attempts of synthesis of high-molecular Almazov through transformation at thermodynamic equilibrium proved fruitless. However, in the work McKervey et. al.12it was reported about the method of synthesis of antitestamentary of 1,6-dicarboxylate with low yield of the reaction product (for example, ˜10%), in which when performing final operations of synthesis was used in the process of rearrangement in the gas phase over a platinum catalyst at a temperature of 360°C. it is Obvious that the use of such source materials in conjunction with its low availability makes this procedure for the synthesis of commercially depriv Catalinas, and, in addition, it does not provide the possibility of synthesis of other tetramantane or other high-molecular Almazov.

Based on the foregoing, in the prior art, there is a real need for compositions containing tetramantane and other high-molecular alasoini. Given the difculties in the synthesis, there is also a need to create ways to extract tetramantane and other high-molecular Almazov from natural sources.

The INVENTION

The present invention relates to new methods of obtaining compositions enriched in high molecular almatadema, from the source of hydrocarbons containing recoverable quantities of high-molecular alasoini components.

According to the first aspect of the present invention provides methods for removing at least part of the components of the source reagent having a lower boiling point than the lowest boiling point selected for retrieval component, which represents the high-molecular almasoud, and the subsequent operation of the pyrolytic processing of the initial reagent under conditions in which pyrolytic treated source reagent selected component or components constituting the high-molecular alasoini, remain in to the Icesave, recoverable (recoverable amount). Therefore, according to this first aspect, the present invention relates to a method comprising the following operations:

a) selecting a source reagent containing selected to extract the component or components constituting the high-molecular alasoini, in the amount recoverable;

b) removing a sufficient number of components from the source reagent having a boiling point lower than the lowest boiling point component, representing macromolecular almasoud selected for extraction, in conditions which ensure the preservation of the selected component or components constituting the high-molecular alasoini, in the treated extract the source reagent in the amount recoverable; and

C) heat treatment of the processed source reagent extracted in the above steps b), pyrolysis, at least, a sufficient number of contained components that are not almatadema that allows extracting a selected component or components constituting the high-molecular alasoini, pyrolytic treated source reagent, and the pyrolysis is carried out in conditions which ensure the preservation of the outcome of the second reagent, subjected to a heat treatment, the selected component or components constituting the high-molecular alasoini, in the amount recoverable.

In a usual source of hydrocarbon reagents components having a lower boiling point than the lowest boiling temperature of the selected component, representing macromolecular almasoud, usually contain components that are not almatadema and components, representing a low-molecular alasoini. Therefore, according to another aspect of the present invention proposes a method of extracting a composition enriched in one or more selected components constituting the high-molecular alasoini, including the following:

a) selecting a source reagent containing the selected component or components constituting the high-molecular alasoini, in the amount recoverable, the components that are not almatadema, which have a boiling point both below and higher than the lowest boiling temperature of the selected component, representing macromolecular almasoud, and at least one component containing a low-molecular almasoud;

b) removing from the source reagent sufficient number of components, not Allaudin what almatadema, which have a lower boiling point than the lowest boiling temperature of the selected component, representing macromolecular almasoud, as well as components, representing a low-molecular alasoini, in conditions which ensure the preservation of the selected component or components constituting the high-molecular alasoini, in the source reagent is subjected to processing; and

C) heat treatment specified processed source reagent extracted in the above steps b), pyrolysis, at least, a sufficient number of contained components that are not almatadema that allows extracting the selected components constituting the high-molecular alasoini, from the source reagent is subjected to pyrolytic processing.

The procedures concerning the removal of components with a lower boiling temperature and pyrolysis of the source reagent used interchangeably. Therefore, according to another aspect of the present invention proposes a method of extracting a composition enriched in the selected component or components constituting the high-molecular alasoini, including the following:

a) selecting a source reagent containing the selected component or components, not only the matter of a high-molecular alasoini, in the amount recoverable;

b) heat treatment of the source reagent for pyrolysis, at least, a sufficient number of contained components that are not almatadema that allows extracting a selected component or components constituting the high-molecular alasoini, from the source reagent is subjected to pyrolytic processing, with the specified pyrolysis is carried out in conditions which ensure the preservation of the original reagent, subjected to a heat treatment, the selected component or components constituting the high-molecular alasoini, in the amount recoverable; and

C) removing from the source reagent sufficient number of those remaining after pyrolysis components, which have a lower boiling point than the lowest boiling temperature of the selected component, representing macromolecular almasoud, in conditions which ensure the preservation of the original reagent subjected to processing, the selected component or components constituting the high-molecular alasoini, in the amount recoverable.

However, it is clear that due to its thermal stability of the components remaining after pyrolysis, which have a boiling point less than the most the e low boiling temperature of the selected component, representing macromolecular almasoud contain at least part of the low molecular weight Almazov originally present in the source reagent. Therefore, according to another aspect of the present invention proposes a method of extracting a composition enriched in the selected component or components constituting the high-molecular alasoini, including the following:

a) selecting a source reagent containing the selected component or components constituting the high-molecular alasoini, in the amount recoverable, the components that are not almatadema, and at least one component representing low-molecular almasoud;

b) heat treatment specified source reagent for pyrolysis at least part of the components that are not almatadema, in conditions which ensure the preservation in the specified source reagent, subjected to a heat treatment, the selected component or components constituting the high-molecular alasoini, in the amount recoverable; and

C) removing from the source reagent is subjected to pyrolysis, a sufficient number of components representing a low-molecular alasoini, in terms of providing the processed original reage is the from which can be derived by the selected component or components constituting the high-molecular alasoini.

It is clear that according to all these aspects of the invention, it is possible and often likely that the source reagents containing high-molecular alasoini will contain several components that represent high alasoini, some of which are subject to selection and the selection other to produce should not be. Depending on which of these components constituting the high-molecular alasoini, are present, which of these components is chosen, it is possible that will be unselected high alasoini, having a boiling point lower than the lowest boiling point selected macromolecular Almazov. Can be removed, at least partially, these unselected high alasoini with a lower boiling point along with other components having a lower boiling point, such as low-molecular almatadema.

When using the initial reagents, quite free from substances that are not almatadema to extract components representing tetramantane, and components representing pentameter, the operation of thermal pyrolysis is not always not is required to ensure the efficiency of their extraction. In the case when after the removal of components representing a low-molecular alasoini, the operation of thermal pyrolysis is not used, the components representing tetramantane, and components representing pentameter, can be extracted from treated source reagent disclosed here by way of separation. Accordingly, according to another aspect of the present invention proposes a method of extracting a composition enriched in components representing tetramantane and pentimento, including the following:

a) selecting a source reagent containing components representing tetramantane, and components representing pentameter, in the amount recoverable, and at least one component representing low-molecular alasoini;

b) removing from the source reagent sufficient number of components representing a low-molecular alasoini, under conditions providing the processed source reagent, which can be extracted components represent tetramantane and pentameter; and

C) removing components representing tetramantane and pentimento, processed from the specified source reagent, methods of separation of substances selected from the group consisting of the following way is: chromatography, thermal diffusion, zone cleaning, successive recrystallization and methods of separating substances by size.

In a preferred embodiment of the invention for each of the above methods is used, the source reagent contains at least about 1 ppb (h/bn) (more preferably, at least about 25 ppb and most preferably at least about 100 ppb) selected components constituting the high-molecular alasoini.

In another preferred embodiment, each of the above methods from the source reagent removed a sufficient number of components representing a low-molecular alasoini, to ensure that the content ratio of components representing a low-molecular alasoini (components representing Tremonton, and more low molecular weight compounds), to the contents of the components constituting the high-molecular alasoini (components representing tetramantane and more high-molecular compounds), not exceeding 9:1, more preferably the ratio does not exceed 2:1 and most preferably the ratio does not exceed 1:1.

In another preferred embodiment, each of the above methods after removal from the source is eagent components, representing low-molecular alasoini, in the source reagent is stored components constituting the high-molecular alasoini, in the amount of at least about 10%, more preferably at least 50% and most preferably at least 90% compared to their quantitative content in the source reagent to remove.

In yet another preferred embodiment of the invention after pyrolysis of the source reagent in the source reagent is subjected to pyrolytic processing, stored components constituting the high-molecular alasoini, in the amount of at least about 10%, more preferably at least about 50% and most preferably at least about 90% compared to their quantitative content in the source reagent to pyrolytic processing.

Preferably extracted source reagent obtained by the above methods, is subjected to additional purification by means of chromatography, membrane separation by size, crystallization, sublimation, etc.

According to one aspect of the present invention, related to the received product, we offer a composition containing at least components representing tetramantane and pins shall amantan, moreover, the composition contains components representing tetramantane, in the amount of at least about 10 wt.% and components, representing pentameter, in the amount of at least about 0.5 wt.%, with respect to the total mass of Almazov contained in the composition.

In another preferred embodiment, the present invention features a composition containing at least components representing tetramantane and pentameter, and the composition contains components representing tetramantane, in the amount of at least about 25 wt.%, more preferably in the amount of at least about 50 wt.% and components, representing pentameter, in the amount of at least about 0.5 wt.%, with respect to the total mass of Almazov contained in the composition.

Preferably, the composition further comprises hexameter and heavier components. Most preferably, the components representing hexameter contained in any such composition does not contain maximally Packed cyclohexanone with the chemical formula C26H30and molecular mass equal to 342.

In yet another aspect of the present invention pertaining to the product of the reaction, h is W a preferred composition, at least, components, representing tetramantane and pentameter, and the composition contains components representing tetramantane, in the amount of at least about 10 wt.%, and components, representing pentameter, in the amount of at least about 0.5 wt.%, in relation to the total weight of the composition. More preferably, such compositions contain components representing tetramantane, in the amount of at least about 25 wt.% and most preferably in the amount of at least about 50 wt.%, and components, representing pentameter, in the amount of at least about 0.5 wt.%, in relation to the total weight of the composition.

Preferably, the composition additionally contains components representing hexameter and other more high alasoini.

BRIEF DESCRIPTION of DRAWINGS

In Fig. 1 shows the structure of Almazov in the form of unit cells of the crystal lattice and its relationship with the structure of diamond. In particular, in Fig. 1 shows the relationship of structures Almazov elementary cell of the crystal lattice of the diamond.

In Fig. 2 shows a gas chromatogram of the source reagent in the form of condensate, which is one of the primary source of reagents, the use of avannah in examples (source reagent a).

In Fig. 3 shows the profile of the simulated distillation of the source reagent in the form of condensate, containing by-products of oil refining, which is used in the examples (source reagent B). Depicted values of boiling point are equivalent to the values of temperature at atmospheric pressure.

In Fig. 4 shows the profile of a simulated high-temperature distillation residues enriched almatadema of condensates, which represents the source reagent a and the source reagent B, at atmospheric pressure. This drawing also shows the equivalent values of the boiling temperature at atmospheric pressure, corresponding to the number of carbon atoms in n-paraffins.

In Fig. 5 shows the profiles of gas chromatographic analysis of the distillation fractions containing tetramantane and other high-molecular alasoini that is obtained from the condensate, representing the source reagent A.

In Fig. 6 shows data obtained by preparative capillary gas chromatography for separation of tetramantane. The first column shows the shoulder straps isolated from fraction No. 33 distillation of the source reagent A. the Numbers in bold refer to the maxima (peaks) of tetramantane. The second column shows the peaks corresponding to selected fractions direction is applied in the traps. Peaks marked with numbers (2, 4, and 6), circled correspond to tetramantane. It should be noted that in one of these peaks are both enantiomers of optically active tetramantane.

In Fig. 7 shows the structure of the four isomers of tetramantane, two of which are enantiomers.

In Fig. 8 (a, B, C) shows the micrograph of crystals of tetramantane isolated from the source reagent And by preparative gas chromatography (Fig. 6). Crystal, is shown in Fig. 8A was isolated from fraction No. 2, collected in the trap, crystals, shown in Fig. 8B, were isolated from fraction No. 4, collected in the trap; and crystal, is shown in Fig. 8B was isolated from fraction No. 6, collected in the trap. Since the two enantiomers of tetramantane have the same retention time in GC, the results of which are shown in Fig. 6, one of the crystals contains both enantiomers.

In Fig. 9, Fig. 10 and Fig. 11 shows the retention time in GC almazosoderzhashchego condensate, which is a fraction No. 38 distillation of the source reagent A, obtained by the distillation and purification. It is shown in Fig. 9 chromatogram total ion current obtained by gas chromatography/mass spectrometry (GC/MS) analysis indicates the presence of high-molecular Almazov at levels that allow the implementation is both their selection. In Fig. 10 shows an ion chromatogram obtained by GC/MS analysis (m/z=394), indicating the presence of heptamethine with a molecular mass equal to 394. In Fig. 11 shows chromatograms total ion current (PETE) (TIC)obtained by GC/MS analysis shows the presence of such levels of heptamethine that allow their separation.

In Fig. 12 shows the simulated profile the distillation of high temperature, which as a source of reagent used, the distillation residue of the source reagent B at atmospheric pressure and a temperature of 650°F +. This drawing also shows the target boundary (1-10) separating distillation to ensure the selection of high-molecular Almazov.

In Fig. 13 shows a gas chromatogram of fraction No. 5 distillation, which is a product of the distillation of the source reagent B at atmospheric pressure and a temperature of 650°F + residue from the distillation, which is shown in Fig. 12 and used in example 1.

In Fig. 14 shows selective ion chromatogram obtained by gas chromatography/mass spectrometry (GC/MS) analysis (m/z=394), proving the existence of isomeric garamantes in fraction No. 5 distillation, which is a product of the distillation of the source reagent B at atmospheric pressure and a temperature of 650&x000B0; F + remainder.

In Fig. 15 shows a gas chromatogram retained fraction obtained by distillation of the source reagent B at atmospheric pressure, which is used in example 1 as a starting reagent in pyrolytic processing. Retained fraction is a substance extracted from the distillation column after the distilling process, the source reagent B at a temperature of approximately 650°F.

In Fig. 16 shows a gas chromatogram of the product of pyrolysis of the parent substance of Fig. 15, that is retained fraction distillation of the source reagent B at atmospheric pressure and a temperature of 650°F + residue from distillation, indicating the decomposition of components that are not almatadema.

In Fig. 17 shows a curve chromatographic separation of fraction No. 32, obtained by distillation of the source reagent And representing the condensate by preparative HPLC (high performance liquid chromatography) on ODS (octadecylsilane) column, which shows the selected fraction (1-9).

In Fig. 18 shows the gas chromatogram by which compares fractions No. 32 distillation source of reagent A with its corresponding fraction No. 6 of Fig. 17, obtained by HPLC. Chromatogram of fraction No. 6, obtained by HPLC indicates C ucitelem the enrichment of one component, representing tetramantane.

In Fig. 19 shows the total ion chromatogram of a current obtained by gas chromatography/mass spectrometry (GC/MS) analysis of fraction No. 6, obtained by HPLC (Fig. 17), showing one main component, and selective ion chromatogram of fraction No. 6 (m/z=292), indicating that this component is one of the isomers of tetramantane.

In Fig. 20A shows a gas chromatogram (using plasma-ionization detector PID (FID)) fraction distillation No. 6 (see Table 3B) of the source reagent B at a temperature of 650°F + residue from distillation, and Fig. 20B is a gas chromatogram of the product resulting from the pyrolytic treatment of this source reagent, indicating the decomposition of components that are not almatadema, and on the availability of components representing pentametre, exemestane and maximally Packed heptamethine, in an amount to provide the possibility of their selection.

In Fig. 21 shows a gas chromatogram (using PID (FID)) fraction No. 5 distillation (see Table 3B) of the source reagent B at a temperature of 650°F + residues from distillation and gas chromatogram of the product obtained as a result of its pyrolytic processing, indicating the decomposition of the components, not anlaysis what almatadema, and there are components that represent tetramantane, pentamadine, exemestane and maximally Packed heptamethine, in an amount to provide the possibility of their selection.

In Fig. 22 in an enlarged scale shows a plot of the gas chromatogram of Fig. 21, in the range of from about 22 to 35 minutes, indicating the presence of the resulting product exemestane and maximally Packed garamantes in quantity, which enable their selection.

In Fig. 23 shows a micrograph of two cocrystallization of pentimento derived from the source reagent A.

In Fig. 24 shows the mass spectrum of the product of pyrolysis fractions No. 6 distillation of the source reagent B at a temperature of 650°F + residue from distillation to indicate the presence of isolated from it cleaned heptamethine with a molecular mass equal to 448.

In Fig. 25 shows the mass spectrum of the product of pyrolysis fractions No. 6 distillation of the source reagent B at a temperature of 650°F + residue from distillation to indicate the presence of isolated from it cleaned otamatone with a molecular mass equal to 446.

In Fig. 26 shows the mass spectrum of the product of pyrolysis fractions No. 6 distillation of the source reagent B at a temperature of 650°F + residue from distillation to indicate the presence of isolated from it cleaned diamantane with molekulyarnoi mass, equal to 456.

In Fig. 27A shows a micrograph of crystals of pansamantala No. 1 (molecular weight equal to 344), isolated from the source reagent B by way of preparative capillary gas chromatography.

In Fig. B shows the total ion chromatogram of a current obtained by gas chromatography/mass spectrometry (GC/MS) analysis, and Fig. 27B shows the mass spectrum, indicating the purity of this selected pansamantala.

In Fig. 28A shows a micrograph of crystals of exemestane No. 8 (molecular weight equal to 396), isolated from the source reagent B by way of preparative capillary gas chromatography.

In Fig. 28B shows the total ion chromatogram of a current obtained by gas chromatography/mass spectrometry (GC/MS) analysis, and Fig. 28C shows the mass spectrum, indicating the purity of this selected exemestane.

In Fig. 29A shows a micrograph of crystals maximally Packed heptamethine (molecular weight equal to 394), isolated from the source reagent B by way of preparative capillary gas chromatography.

In Fig. 29B shows the total ion chromatogram of a current obtained by gas chromatography/mass spectrometry (GC/MS) analysis, and Fig. 29B shows the mass spectrum, indicating the purity of E. the CSOs selected heptamethine.

In Fig. 30 is a table that specifies the list of Almazov with different molecular weight contained in each family of high-molecular Almazov, and the values of their molecular weight.

In Fig. 31 is a diagram of distillation, which shows the fraction distillation of the source reagent containing high-molecular alasoini selected so that to provide appropriate enrichment various selected high-molecular almatadema.

In Fig. 32 and Fig. 33 charts showing the sequence of elution of many individual molecular Almazov on two different chromatographic columns: UDF (octadecylsilane) and Hypercarb.

In Fig. 34 is a diagram of a sequence of operations, which shows the various operations used in the process of separating the fractions containing high molecular weight alasoini, and the individual components constituting the high-molecular alasoini. It should be noted that, as described in the examples, in some cases, can be used by different sequence to perform these operations, and some operations can be skipped.

In Fig. 35A and Fig. 35B shows the combined data about the properties of various high-molecular Almazov of this proposal, obtained by the result of the m gas chromatography/mass spectrometry (GC/MS) analysis and HPLC.

In Fig. 36 illustrates the concept HPLC on two columns used to separate tetramantane and pentimento.

In Fig. 37A and Fig. B shows the data obtained by preparative capillary gas chromatography, which is used to highlight exemestane. In Fig. 37A is shown separated from the source reagent B through the first column that contain exemestane two types. In Fig. B shows peaks selected by the second column and sent in traps. Through this procedure was carried out highlighting exemestane in its pure form, namely exemestane No. 2, which represents the second eluting hexameter in a given sample, subjected to gas chromatography/mass spectrometry (GC/MS) analysis, and exemestane No. 8, elution of which is the eighth in order.

In Fig. 38A shows a micrograph of the crystal nanananana.

In Fig. 38B shows the mass spectrum of the dissolved crystal nanananana.

In Fig. 39A shows the results of gas chromatography/ mass spectrometry (GC/MS) analysis of isolated maximally Packed diamantane, and Fig. 39B shows the mass spectrum of this substance.

In Fig. 40A shows a micrograph of the crystal maximally Packed Diamantina.

In Fig. 40B shows the mass-SP the CTD dissolved crystal diamantane of Fig. 40A.

DETAILED description of the INVENTION

The present invention provides methods of extraction and purification of the components constituting the high-molecular alasoini, from the source of hydrocarbon reagents, and compositions containing such high alasoini. However, before that, as will be discussed more detailed description of this invention, you must first define the following terms.

Used herein the following terms have the following meanings.

The term "almasoud" ("diamondoid"refers to substituted and unsubstituted in the lattice compounds adamantanol series, including adamantane, diamantane, Tremonton, tetramantane, pentimento, hexameter, garamantian, octameter, monumental, Diamanten, undocumented, etc. and all their isomers and stereoisomers. Substituted alasoini preferably contain from 1 to 10 and more preferably 1-4 alkyl replacement groups.

The term "components representing a low-molecular alasoini," or "components constituting the adamantane, diamantane and Diamanten" refers to any and/or all of unsubstituted and substituted derivatives of adamantane, diamantane and Tramontana.

The term "components constituting the high-molecular alasoini," refers to any and/or all substituted and unsubstituted diamond is idam, relevant tetramantane or more macromolecular compounds, including tetramantane, pansamantala, hexamethonium, heptaminol, okhamandal, nanananana, Diamantina, undecalactone etc., including all their isomers and stereoisomers. Preferred high molecular weight alasoini" include substituted and unsubstituted tetramantane, pentamadine, exemestane, heptamethine, otamatone, nanananana, documentary and undocumentary. In Fig. 30 is a table that specifies the list of high-molecular Almazov and the values of their molecular weight.

The term "component, representing tetramantane," refers to any and/or all substituted and unsubstituted to almatidan, relevant tetramantane.

The term "component, representing pentimento," refers to any and/or all substituted and unsubstituted to almatidan, relevant pentimento.

The term "component, representing the unionised alasoini," refers to the components constituting the high-molecular alasoini, which have no charge, such as positive charge generated during mass spectrometric analysis, with the phrase "components constituting the high-molecular alasoini," is above a certain value.

The term "components, represents the substance of a unionised tetramantane," refers to the components, representing tetramantane, which have no charge, such as positive charge generated during mass spectrometric analysis.

The term "component, representing the unionised pentameter, and components representing unionised alasoini, which is heavier than pentameter," refers to the components representing pentameter, and to the components representing more high alasoini than pentameter, without charge, for example, the positive charge generated during mass spectrometric analysis.

The terms "selected components constituting the high-molecular alasoini," etc. refer to one or more substituted or unsubstituted macromolecular almatidan that it is desirable to allocate or "enrich" their product.

The term "unselected components constituting the high-molecular alasoini,etc. refer to the macromolecular almatidan that are not selected high molecular almatadema".

The term "enriched" when used to describe the level of purity of one or more components constituting the high-molecular alasoini, refers to such substances, which are at least partially separated from the original Rea the enta, and in the case of the use of the term "enriched" for the individual components constituting the high-molecular alasoini, this means that their concentration is increased, at least 25, preferably at least 100 times compared with their initial concentration in the source reagent. Preferably "enriched" macromolecular almasoud or "enriched" components constituting the high-molecular alasoini constitute at least 25%, especially at least 50% (that is 50%-100%), more preferably at least 75% and most preferably at least 95 wt.% or even at least 99 wt.% from the total mass of matter in which they are present, or, in other words, have a purity of at least, 25%, 50%, 75%-95% or 99% relative to the mass of the substance.

The term "source reagent" or "source of hydrocarbon reactant" refers to a hydrocarbon material containing a high-molecular alasoini in amounts recoverable (recoverable amount). Preferably such source reagents include oil, natural gas liquids, flows of oil products, oil, extracted from the rock collector, oil shale, tar Sands, from source rocks and other Such components are typically, but not necessarily, contain od is n or more components, representing low-molecular alasoini, as well as components that are not almatadema. The latter usually differ that contain components having a boiling point both below and higher than the lowest boiling point corresponding to tetramantane, which is at atmospheric pressure boils at approximately 350°C. a Typical source reagents may also contain impurities such as sediment, metals, including Nickel, vanadium, and other inorganic substances. They can also contain heteromolecular containing sulfur, nitrogen, etc. All these substances, which are not almatadema, see "components that are not almatadema", with the meaning of the latter term is defined above.

The term "unselected substances" refers to the set of components of the original reagent, which are not selected high molecular almatadema" and contain components that are not almatadema", "low-molecular alasoini" and "unselected high alasoini", as defined here, the meaning of these terms.

The term "remove" or "removal" refers to removal processes from the source reagent components that are not almatadema, and/or components, representing a low-molecular alasoini, and/or components, representing navipane the high alasoini. These processes include, but are not limited to, methods of separation by size, distillation, evaporation under normal and under reduced pressure, the separation by means of separators installed at the mouth of wells, extraction, chromatography, chemical extraction, crystallization and the like, for Example, Chen, et al.4reveal the processes of distillation to remove adamantane substituted adamantane, diamantane, substituted diamantane and Tramontana from the source of hydrocarbon reactant. Methods of separation by size include methods of separation by membranes, molecular sieves, gel permeation separation methods suitable for displacement chromatography size, etc.

The term "distillation" or "distillation operation" refers to the process of distillation of the original hydrocarbon reactant at atmospheric pressure, under reduced pressure and at elevated pressure, which perform in conditions that ensure the completion of the distillation after removal of the source reagent part, and preferably at least 50 wt.% components constituting the adamantane, diamantane and Tremonton. Unless otherwise specified, the temperature of distillation is provided in the form of equivalent values of temperature at atmospheric pressure.

The terms "division of fractions" and "operation of fractionation" refers to PR is the processes, through which provide separation of the substances contained in the mixture of substances between them, for example, due to different solubility, different vapour pressure of various chromatographic affinity, etc.

The term "heat treatment for pyrolysis" and the like refer to the heat source reagent or fraction of the original reagent at atmospheric pressure, under reduced pressure or under increased pressure to ensure pyrolysis of the one or more components contained in the initial reactant.

The term "component of the original reagent, non-almatadema," refers to the components of the source reagent or fraction of the original reagent, which are not, in fact, almatadema in accordance with the term "almasoud", as defined above.

The term "saved" is to preserve at least part of the components constituting the high-molecular alasoini contained in the extracted source reagent, compared with the number these Almazov contained in the primary source reagent. In a preferred embodiment of the invention in the extracted source reagent retain at least about 10 wt.% components constituting the high-molecular alasoini, more preferably at least about 50 the EU.% components representing high alasoini, and most preferably at least about 90 wt.% components constituting the high-molecular alasoini, and each of these values is given in relation to the total number of such Almazov contained in the source reagent before processing.

The term "chromatography" refers to any one of a number of known methods, chromatography, including, but not limited to, chromatography on columns or chromatographic separation by density (either normal or reverse phase), gas chromatography, high performance liquid chromatography (HPLC), etc.

The term "alkyl" refers to saturated aliphatic groups, unbranched and branched chains that typically contain from 1 to 20 carbon atoms, most preferably 1 to 6 carbon atoms ("lower alkali"), and cyclic saturated aliphatic groups typically contain from 3 to 20 carbon atoms and preferably from 3 to 6 carbon atoms (also referred to as a "lower alkilani"). As an example, the terms "alkyl" and "lower alkyl" can be such radicals as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

The method

The methods according to the but this invention can be implemented using readily available starting materials described by the following General methods and procedures. It is clear that in cases where the typical or preferred process conditions (i.e., the values of the reaction temperature, duration of reaction, solvents, pressures, etc. can be also used, and other process conditions, unless otherwise noted. Optimum reaction conditions may vary depending on the source of the reagents, but these conditions can be determined by an expert in the field of technology through the conventional optimization methods.

In addition, high-molecular alasoini of this invention typically contain one or more isomers or stereoisomers, and substituted alasoini typically contain one or more centers of chirality. Therefore, if necessary, these compounds may be derived or isolated in the form of pure isomers or stereoisomers, for example in the form of the individual enantiomers or diastereoisomers, or as mixtures enriched stereoisomers. All such isomers and stereoisomers (and enriched their mixtures) are included in the scope of the present invention, unless otherwise indicated. Pure stereoisomers (or choke) can be obtained, for example, crystallization of optically active solvent or stereotypically reagents that are well known in the art. Alternative RA is a division of racemic mixtures of such compounds can be carried out using, for example, chiral chromatography on columns, chiral separating agents, etc.

In the methods according to the present invention the selection of the source reagent is carried out in such a way that the specified source reagent contains one or more selected components constituting the high-molecular alasoini, in the amount recoverable. Preferably such source reagent contains one or more components constituting the high-molecular alasoini, in the amount of at least about 1 ppb (h/bn), more preferably at least about 25 ppb and most preferably at least about 100 ppb. Of course, it is clear that the use of initial reagents, with a higher concentration of the components constituting the high-molecular alasoini, facilitates the extraction of these components.

The preferred source reagents include, for example, condensates, natural gas and flows of refined petroleum products having a high concentration of high-molecular Almazov. In the latter, such flows of oil products include flows of hydrocarbons extracted in the process of cracking, distillation, coking, etc. are Particularly preferred source reagents include the original reagents, representing ashcontent, extracted from the reservoir Norfleet (Norphlet) in the Gulf of Mexico and from the reservoir LeDuc (LeDuc) in Canada.

In one embodiment, the initial reagents used in the methods according to the present invention, usually contain components that are not almatadema, which have a boiling point both below higher than the lowest boiling point selected for retrieval component, which represents the high-molecular almasoud, and one or more components representing a low-molecular alasoini. These initial reagents usually contain a mixture of high-molecular Almazov. Some of these high-molecular Almazov can have a lower boiling point than the boiling point of the selected almasoud that depends on what high alasoini are selected. As a rule, selected to retrieve the component representing macromolecular almasoud with the lowest boiling point has a boiling point greater than about 335°C. In a typical source reagents, the ratio of the concentration of low molecular weight Almazov to the concentration of high molecular weight Almazov is usually about 260:1 or more. In addition, as shown in Fig. 20 and Fig. 21, a typical source reagents containing components present is which is a high molecular weight alasoini, also contain components that are not almatadema.

In such initial reagents often cannot be achieved effectively removing selected components constituting the high-molecular alasoini, directly from the source reagent due to their low concentration relative to the concentration of unselected components. Therefore, the methods of the invention can include removal from the source reagent sufficient quantities of these impurities in the conditions ensuring the possibility of obtaining the processed source reagent, which can be extracted is selected components constituting the high-molecular alasoini.

In one embodiment, the implementation of the removal of impurities includes the operation of the distillation of the source reagent to remove components that are not almatadema, and components representing a low-molecular alasoini, and in some cases also other unselected high-molecular Almazov, having a boiling point less than the boiling point selected for retrieval component, which represents the high-molecular almasoud with the lowest boiling point.

In a particularly preferred embodiment, the operation of the distillation of the source reagent is performed in such a way as to obtain a fraction having equival NTUU boiling temperature at atmospheric pressure is higher and lower, than approximately 335°C, more preferably equivalent to the boiling point at atmospheric pressure is higher and lower than approximately 345°C. In any case, the low-temperature fraction, which is enriched in low molecular weight almatadema, and components that are not almatadema, which have a lower boiling point, taken from the top of the column and removed and the fractions with higher boiling point, which is enriched in high molecular almatadema retain. Of course, it is clear that the temperature boundaries boiling fractions during distillation is a function of pressure and that the above temperatures are equivalent temperatures at atmospheric pressure. The presence of reduced pressure leads to the same boundary boiling fractions obtained when a lower distillation temperature, whereas the presence of high pressure leads to the same boundary boiling fractions obtained when a higher temperature distillation. The relationship between pressure/temperature distillation at atmospheric pressure and pressure/temperature distillation under reduced pressure or at elevated pressures is well known to specialists in this field of technology.

The distillation can be carried out in such a way as to ensure the separation of IP is one of the reagent into fractions with multiple factions in a certain temperature range to provide primary enrichment of selected high-molecular almatadema or groups selected macromolecular Almazov. Fractions enriched in one or more selected almatea or specific component, representing almasoud, retain, this may require additional cleaning. The following table shows the typical boundaries of separation into fractions (equivalent to the boiling temperature at atmospheric pressure), which can be used for enrichment of fractions taken from the top of the column, various high-molecular almatadema. In practice, it may be appropriate to split into fractions in a wider temperature range, which will often contain a group of high-molecular Almazov, which separation may be performed in subsequent operations division.

Boundaries of separation into fractions

Most preferred optionThe preferred optionUseful option
Macromolecular almasoudThe lower the temperature of the sampling fraction(°C)The top temperature of the sampling fraction(°C)The lower the temperature of the sampling fraction(°C)The top temperature of the sampling fraction(°C)The lower temperature is round selection fraction(° C)The top temperature of the sampling fraction(°C)
Tetramantane349382330400300430
Pansamantala385427360450330490
Cyclohexadecane393466365500330550
Exemestane393466365500330550
Heptamethine432504395540350600
Otamatone454527420560375610
Nonmonetary463549425590380650
Documentary472571435610390660
Undocumentary499588455625400675

It should be understood that the presence of substituted high molecular Almazov moreprivate the relative shift of these preferred temperatures in the higher temperature region due to the addition of substitute groups. Additional operations the temperature of cleaning can get the fractions containing the required almasoud, with a higher degree of purity. In Fig. 31 provides additional explanation of how due process of fractionation can be obtained fractions enriched in individual or multiple components representing high alasoini.

In addition, it should be understood that the process of fractionation can be stopped before it made the selection of the selected high molecular almasoud from the top of the column. In this case, the high-molecular almasoud may be separated from the remainder obtained as a result of fractionation.

Other ways to remove low molecular weight Almazov, unselected high-molecular Almazov, if any, and/or hydrocarbon components that are not almatadema include the following methods, listed only as non-limiting examples: methods of separation by size, evaporation or normal, or under reduced pressure, sublimation, crystallization, chromatography, separation at the wellhead, the use of reduced pressure, and the like, for Example, in a preferred embodiment, the removal of low molecular weight Almazov of initial reagents can be carried out by the plural is and ways. First, in the commercial production of gas and liquids, crystallization may occur adamantane and diamantane dissolved in depth gases due to pressure reduction. Commercially available separators installed in the wellhead, provide effective removal of low molecular weight Almazov from such feedstock in order to avoid problems caused by the deposition of sediment in operating the equipment in the commercial production of oil and gas. Other removal processes to ensure selection of the source of raw materials of low molecular weight Almazov can be used the fact that molecules of high molecular weight Almazov are large. For example, methods of separation by size using membranes allow selective transmission of low molecular weight Almazov contained in the feedstock is held by the membrane, through the membrane barrier, provided that the pore size of the membrane barrier is chosen in such a way as to distinguish between compounds with a high molecular alasoini components, compared with components representing a low-molecular alasoini. To ensure the separation of substances in size can be also used molecular sieve with an appropriate pore size, for example, C is ality etc.

In a preferred embodiment, the process results in the removal get processed source reagent, in which the ratio of the components constituting the low-molecular alasoini to the components constituting the high-molecular alasoini, does not exceed 9:1, more preferably does not exceed 2:1 and most preferably does not exceed 1:1. Even most preferably, after removal of the initial reagent component(s)that represent(s) a low-molecular almasoud, in the source reagent retain at least about 10%, more preferably at least 50% and most preferably at least 90% of the components constituting the high-molecular alasoini, compared with the number contained in the source reagent to the delete operation.

In the case where it is desirable to carry out the extraction exemestane and components constituting the high-molecular alasoini, the source reagent is usually subjected to and operation of pyrolysis to ensure the removal of the source reagent, at least part of the hydrocarbon components, which are not almatadema. The pyrolysis process provides an effective increase in the concentration of high molecular weight Almazov contained in the source reagent is subjected to the feast of the political process, thereby allowing to carry out their removal.

The pyrolysis is performed by heating the source reagent under vacuum or in an atmosphere of inert gas at a temperature of at least about 390°C, preferably from approximately 400°C to about 500°C, more preferably from about 400°C to about 450°C and most preferably in the range of 410°C-430°C, over a period of time sufficient to perform a pyrolysis at least part of the components the source reagent, non-almatadema. The choice of the specific mode of conduct in such a way as to ensure the preservation of the original reagent components constituting the high-molecular alasoini, in the amount recoverable. The method of selection of these modes is well known to specialists in this field of technology.

Preferably, the pyrolysis process is continued for a sufficient period of time and at a sufficiently high temperature to ensure thermal decomposition of at least approximately 10% of components that are not almatadema (more preferably, at least about 50% and most preferably at least about 90%), from the source reagent is subjected to pyrolytic processing, is compared to the total mass of the components, non-almatadema contained in the source reagent prior to pyrolysis.

In yet another preferred embodiment of the present invention after operation of the pyrolysis of the source reagent in the source reagent is subjected to pyrolytic processing, retain at least about 10%, more preferably at least about 50% and most preferably at least about 90% of the components constituting the high-molecular alasoini, compared with the number contained in the source reagent to pyrolytic processing.

In a preferred embodiment of the present invention the delete operation from a source of low molecular weight reagent Almazov and hydrocarbon components, which are not almatadema, with a low boiling point to perform operations pyrolytic processing. However, it is clear that these procedures can be performed in reverse order, with the operation of the pyrolysis produce before surgery removal of low molecular weight Almazov from the source reagent.

Although the preferred implementation of the present invention includes the operation of pyrolysis, it is not always necessary. This is because some of the original reagents can have the high the concentration of high molecular weight almasoud, therefore, for the selection of components constituting the high-molecular alasoini, the source reagent is subjected to processing (i.e. after the removal of components representing a low-molecular alasoini)may be directly subjected to purification methods such as chromatography, crystallization, etc. However, when the concentration or the degree of purity contained in the source reagent components constituting the high-molecular alasoini is insufficient for such extraction, use the pyrolysis operation.

Even in the case of the operation of pyrolysis, it is preferable to carry out additional cleaning of the extracted source reagent using one or more purification methods, such as chromatography, crystallization, methods based on thermal diffusion, zone cleaning, successive recrystallization, distillation size, etc. In the most preferred method extracted the source reagent is first subjected to separation by density by way of chromatography columns using silica gel impregnated with silver nitrate, and then produce a selection of target Almazov by HPLC on two different columns with different selectivity and crystallization to obtain crystals televi the high-molecular Almazov in pure form. In those cases, when the concentration of high molecular weight Almazov is not high enough for crystallization, it may be necessary additional enrichment implemented, for example, by preparative capillary gas chromatography.

Structures

The above methods provide new compositions containing high molecular weight alasoini. For example, in one embodiment, the implementation of these methods provide a composition containing at least components representing tetramantane and pentameter, while the composition contains components representing tetramantane, in the amount of at least about 10 wt.%, and components, representing pentameter, in the amount of at least about 0.5 wt.% in relation to the total number of components present, representing alasoini. Alternatively, the compositions according to the present invention contain components representing tetramantane, in the amount of at least about 10 wt.%, and components, representing pentameter, in the amount of at least about 0.5 wt.% by weight of the total composition.

In a preferred embodiment of the present invention the composition contains at least components is s, representing tetramantane and pentameter, while the composition contains components representing tetramantane, in the amount of at least about 25 wt.% and components, representing pentameter, in the amount of at least 1 wt.% in relation to the total number of components present, representing alasoini, most preferably components representing tetramantane, in the amount of at least about 50 wt.% and components, representing pentameter, in the amount of at least 1 wt.% in relation to the total number of components present, representing alasoini.

In another preferred embodiment of the present invention the composition contains at least components representing tetramantane and pentameter, while the composition contains components representing tetramantane, in the amount of at least about 25 wt.% and components, representing pentameter, in an amount constituting at least 1 wt.% in relation to the total weight of the composition, and most preferably components representing tetramantane, in the amount of at least about 50 wt.% and components, representing pentameter, in quantity, less than the least 1 wt.% in relation to the total weight of the composition.

In addition to the components representing tetramantane and Panamanian contained in these compositions, the compositions preferably additionally contain components representing hexameter, most preferably one or more components representing garamantian, octameter, monumental, deimantas and undocumented. More preferably, the components representing hexameter contained in any such composition does not contain maximally Packed cyclohexanone with the chemical formula C26H30and molecular mass equal to 342.

In the further purification of these compounds have the composition that contains at least approximately 50% or more components representing tetramantane (either as individual isomers or as mixtures of isomers tetramantane), components representing pentameter (either as individual isomers or as mixtures of isomers pansamantala), components representing hexameter (either as individual isomers or as mixtures of isomers exemestane), components representing garamantian (either as individual isomers or as mixtures of isomers heptamethine)components representing octameter (either in the form of individual who's isomers, either in the form of a mixture of isomers otamatone), components representing monumenten (either as individual isomers or as mixtures of isomers nanananana), components representing Diamanten (either as individual isomers or as mixtures of isomers diamantane), etc.

The above compositions contain components that represent high alasoini in unionised form.

Utility

The methods of the present invention provide compositions with increased concentration of (enriched) macromolecular Almazov. These high-molecular alasoini suitable for use in microelectronics, molecular electronics and nanotechnology. In particular, properties such as stiffness, strength, stability, conductivity, presence of a variety of structural forms and many centers accession possessed by these molecules makes it possible to create a reliable, durable and high precision devices with nanometer dimensions.

In addition, these high-molecular alasoini can also be used as part of a high quality lubricant with high viscosity index and very low pour point.13This is because these fluids contain a liquid having viscosity of the lubricant, and the t of approximately 0.1 to 10 wt.% Almazov.

In addition, these high-molecular alasoini can be used as fuel in high-density method described by Chung et al.14, which is incorporated here by reference.

The following examples are presented to illustrate the present invention and in no way should be interpreted as limiting the scope of patent claims of the present invention. All temperatures are given in degrees centigrade, unless otherwise indicated.

EXAMPLES

The following abbreviations used in this description and in the drawings have the following values. Any reduction that is not listed below, has a common value.

API)=American petroleum Institute;
EQ ATM (atm eqv)=the equivalent value at atmospheric pressure;
mod (btms)=the residue from distillation;
The FINAL OTB fractions (EOR Traps)=the end of the sampling fractions;
PID (FID)=a flame ionization detector;
g (g)=grams;
GC (GC)=gas chromatography;
GC/MS (GC/MS)=gas chromatographic/mass spectrometric analysis;
hour (h)=h;
HPLC (HPLC)=high-performance liquid chromatography;
Please take AREA (HYD RDG)=the reading of the hydrometer;
l (L)=liter;
min (min)=minute;
ml (mL)=milliliter;
mmol (mmol)=millimoles;
H (N)=normal;
PA (PA)=picoampere;
mltc (ppb)=billionth (h/bn);
ppm (ppm)=millionth part (h/bn);
PP (RI)=the refractive index;
IMIT LANE (SIM DIS)=simulated distillation;
The BEGINNING (ST)=beginning;
PETE (TIC)=total ion current;
TLC (TLC)=thin-layer chromatography;
TPDT (VLT)=the temperature in the wire;
ABOUT/ABOUT (VOL PCT)=volume/volume;
About sod (v/v)=volume %;
weight (wt)=weight;
WEIGHT CRL (WT PCT)=weight percent.

Introduction

Was carried out the isolation and crystallization of the following components constituting the high-molecular alasoini: all tetramantane isolated from both the initial reagents a and B, all pentimento (with molecular weight equal to 344), isolated from the source reagent B, two crystals exemestane (with molecular weight equal to 396), isolated from the source reagent B, two crystals heptamethine (with molecular weight equal to 394), isolated from the source reagent B, crystal octomania (with molecular weight equal to 446), isolated from the source of reagent b were isolated from the source reagent B crystal nanananana (with molecular weight equal to 498) and crystal diamantane (with molecular weight equal to 456). By procedures described in these examples may also be implemented allocation and other components constituting the high-molecular alasoini.

Operations used in various PR the measures schematically shown in Fig. 34.

Example 1 describes the most generic way to select components that represent high alasoini, which can be used for all reagents. In this way the final allocation (step 7, Fig. 34) is performed by using HPLC.

In example 2 described variant of the method of example 1, in which the final allocation (step 7, Fig. 34) is carried out using preparative gas chromatography instead of HPLC.

In example 3 described variant of the method of example 1, in which the operation of pyrolysis (5, Fig. 34) do not perform. As shown in Fig. 34, an optional allocation by liquid chromatography (step 6, Fig. 34) also do not perform. These variants of the method, in General, apply only to some of the initial reagents, and they are usually used in those cases when it is intended to highlight the high-molecular almatadema are tetramantane, pentimento and cyclohexanone.

Example 4 describes another variant of the method 1, in which the final products obtained in examples 1 and 3 was subjected to purification by preparative gas chromatography (step 8, Fig. 34) for further separation of the components constituting the high-molecular alasoini.

In the use of the e 5 describes the process of pyrolysis fractions No. 5 of the distillation of the source reagent B.

Example 6 describes the process of removing substances that are not almatadema by pyrolysis in the allocation of tetramantane.

Example 7 describes the selection process tetramantane using HPLC.

In example 8 the procedure of analysis of the source reagents enriched in high molecular almatadema.

In example 9 describes the enrichment process components representing pentameter, and their identification using gas chromatography.

In example 10 demonstrated the presence of garamantes, artamanov and Diamantino in the products of pyrolysis.

In examples 11A and 11B and 11B described the enrichment process components representing garamantian, and their selection.

In examples 12A and 12B described the enrichment process components representing octameter, and their selection.

In examples 13A and 13B described the enrichment process components representing monumental, and their selection.

In examples 14A and 14B described the enrichment process components representing Diamanten, and their selection.

In example 15 describes the process of enrichment components representing undocumented, and their selection.

It is clear that you can change the order of execution of various operations, distillation, chromatography and pyrolysis, although the order of execution specified in Example 1, gives the best is their results.

EXAMPLE 1

This example contains seven operations (see diagram of the sequence of operations in Fig. 34).

Operation 1.The choice of the source reagent
Operation 2.Performing gas chromatography/mass spectrometry (GC/MS) analysis
Operation 3.Distillation of the source reagent at atmospheric pressure
Step 4.Vacuum separation into fractions of the distillation residue at atmospheric pressure
Operation 5.Pyrolysis of selected fractions
Operation 6.Removal of aromatic and polar components, which are not almatadema
Operation 7.The selection of high-molecular Almazov by HPLC on many columns:

a) through a first column having a first selectivity, get fractions enriched in specific polymer sciense ser-lar-almatadema;

b) through a second column of different selectivity, get a dedicated high alasoini.

This example formulated Pimentel is allocating a number of exemestane. In examples 5-15 demonstrated that this method can easily be adapted to highlight other macromolecular Almazov.

Step 1 - select the source reagent

Were obtained corresponding to the source material. These substances include the source reagent And representing the condensate (Fig. 2), and the source reagent B, representing a condensate containing oil components. Although he could be used and other condensates, petroleum products or shoulder straps and products of oil refineries, the choice of these two substances was due to the presence of high concentration of Almazov that high molecular weight Almazov is approximately 0.3 wt.%, that was determined by the results of gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS) analysis. Both the source reagent had bright colour and had a gravity of ANI in the range from 19° to 20° API.

Step 2 - Perform gas chromatography/mass spectrometry (GC/MS) analysis

Was gazohromatografichesky/mass spectrometry (GC/MS) analysis of the source reagent And to confirm the presence of the target high-molecular Almazov and get the values of the retention time of these target compounds by gas chromatography. This information what I was used to track a single target high molecular Almazov subsequent selection procedures. In Fig. 35A shows a table that lists typical data GC/MS analysis of samples of exemestane (the values of the retention time in GC, mass spectral molecular ion (M+) and the main peak (maximum)). This table (Fig. 35A) also contains similar information about the results of the GC/MS analysis of other high-molecular Almazov. Although the relative retention times in GC are approximately the same, the retention time in GC samples, not shown in the table change over time. It is recommended to perform regular updates of data values GC/MS analysis, especially in the case of detection of the shift of the retention time in GC.

Step 3 - Distillation of the source reagent at atmospheric pressure

Sample source reagent B was subjected to distillation into several fractions according to their boiling point to separate components with lower values of the boiling point (components that are not almatadema, and low molecular weight Almazov) and to further increase the concentration of specific Almazov and to enrich their various factions. The output of the fractions distilling at atmospheric pressure for two separate samples of the source reagent B is shown in the following Table 1 and compared with the yield of products obtained by simulated re once. From Table 1 it is evident that the data obtained by simulated distillation, are consistent with data from real distillation. Data obtained by simulated distillation, were used for subsequent planning processes distillation.

Table 1
The output of the fractions distilling at atmospheric pressure for two separate runs of the original reagent B
Fraction (°F)Estimated value of the output product at IMIT LANE (in wt.%)The source reagent B (Run No. 2) (wt.%)The difference
To 3498,07,60,4
from 349 to 49157,057,7a-0.7
from 491 to 64331,030,60,4
643 and above4,04,1-0,1

Fraction (°F)Estimated value of the output product at IMIT LANE (in wt.%)The source reagent B (Run No. 1) (wt.%)The difference
To 47763,259,3a 3.9
from 477 to 5154,87,3 a-2.5
from 515 to 64928,531,2-2,7
649 and up3,52,11,4

Step 4 - the Division of the residue of the distillation at atmospheric pressure into fractions by vacuum distillation

The resulting Operation 3 the residue from the distillation of the source reagent B at atmospheric pressure (containing 2-4 wt.% primary source reagent) was subjected to distillation into fractions containing high molecular weight alasoini that shown in Fig. 12 and Fig. 31. The starting material for this process is the distillation of high temperature was the result of distillation at atmospheric pressure and a temperature of 650°F + remainder. Full protocols distillation of the source reagent B are shown in tables 2A and 2B. In tables 3A and 3B shows the protocols vacuum distillation of the source reagent B at a temperature of 650°F + residues from distillation.

Table 2A: Protocol distillation of the source reagent B

The source reagent B

Used column: Clean, size 9 inches × 1.4 inches, from attachment tabs

tr>  
DATA OBTAINED from the DISTILLATIONNORMALIZE-ENThe TRUE-CUE
FACTIONThe EVAPORATION TEMPERATURE of the INITIAL-FINALMASS, gVOLUME, ml at 60°FAPI 60/60DENSITY at 60°FWEIGHT %ABOUT %WEIGHT %ABOUT %
1226-34967,08038,00,8348to 7.618,547,39compared to 8.26
2349-491507,755422,80,917057,6559,1255,9857,23
3491-643269,62689,11,006430,6228,6029,7327,69
HOLDING COLUMN0,206,61,02460,020,000,020,00
BALANCE643+36,1356,61,02464.09 to3,743,983,62
The END of the SAMPLING FRACTIONS0,000,000,000,00
TOTAL880,6937100,00100,0097,0996,80
LOSS26,4312,913,20
The ORIGINAL SUBSTANCE907,096819,50,9371100,00100,00
VALUES API) AND the DENSITY OBTAINED BY the INVERSE CALCULATION19,10,9396

Table 3B: Protocol distillation of the source reagent B and the balance

<> The source reagent B Is the Residue after distillation at atmospheric pressure and a temperature of 650°F + balance

Used column: Sarnia Hi Vac

the 5.25
FACTIONThe EVAPORATION TEMPERATURE of the INITIAL-FINALMASS, gVOLUME, ml at 60°FAPI 60/60DENSITY

at 60°F
WT.%VOL.%WT.%VOL.%
1601-656666,46394,11,043520,1219,3820,0319,40
2656-702666,96465,61,032120,1419,5920,0519,62
3702-752334,33308,31,0122to 10.0910,01of 10.0510,02
4752-800167,717314,50,9692of 5.06the 5.255,04
5800-852167,318121,70,9236of 5.055,495,035,50
6852-900167,1181of 21.90,9224of 5.055,495,025,50
7900-950238,4257of 21.20,92677,257,797,177,80
8950-97685,49118,90,94082,58was 2.76to 2.57was 2.76
9976-100080,88518,20,94522,442,582,432,58
101000-102693,89816,90,95352,832,972,822,98
HOLDING COLUMN4,043,41,04890,120,120,120,12
BALANCE1026+621,85933,41,048918,7817,9818,69to 18.01
The END of the SAMPLING FRACTIONS17,8200,540,610,540,61
TOTAL3311,73298100,00100,0099,56100,15
LOSS14,6-50,44-0,15
The ORIGINAL SUBSTANCE 3326,332938,61,0100100,00100,00
VALUES API) AND the DENSITY OBTAINED BY the INVERSE CALCULATION9,41,0039

Table 4
The chemical composition of the source reagent B
The results of chemical analysis of the residue after distillation of the source reagent B at a temperature of 650°F+
Chemical elements obtained in the measurement resultValue
Nitrogen0,991 wt.%
Sulfur0,863 wt.%
Nickel8,61 ppm (part per million)
Vanadium< 0.2 ppm) (ppm)

Table 4 shows partial chemical composition of the residue obtained by distillation of the source reagent B at atmospheric pressure (at temperature 650° (F)that contains some of the recognized impurities. Table 4 shows the weight percent of nitrogen, sulfur, Nickel and vanadium in residual after PE is Agency source reagent B at atmospheric pressure. These substances are removed in subsequent operations.

Operation 5 - Pyrolysis of selected fractions

Pyrolysis and decomposition of part of the components that are not almatadema contained in the various distillation fractions obtained during the operation of 4 (Fig. 34), was used high-temperature reactor, whereby it was provided enrichment distillation residue by almatadema. The pyrolysis process was carried out at a temperature of 450°C for 19.5 hours. Gas chromatogram (PID) fraction No. 6 (see table 3B) shown in Fig. 20A. In Fig. 20B shows a chromatogram of the product of pyrolysis. The comparison of these chromatograms suggests that as a result of pyrolysis was removed much of the hydrocarbons that are not almatadema, and was significantly increased concentration of high-molecular Almazov, especially examintaion. When this operation pyrolysis was used reactor PARR® capacity 500 ml, byPARR INSTRUMENT COMPANY, Moline, Illinois.

Step 6 - remove the aromatic and polar components, which are not almatadema

The pyrolysis product obtained in operation 5, was passed through a chromatographic column filled with silica gel using cyclohexane as a solvent for elution), providing separation by density, for removal of polar compounds the deposits and asphaltenes (6, Fig. 34). The use of silica gel impregnated with silver nitrate (AgNO3, 10 wt.%), secured cleaner almazosoderzhashchikh fractions due to the removal of free aromatic and polar components. Although using this method, the chromatographic separation of aromatic components is not required, it facilitates the execution of subsequent operations.

Operation 7 - Selection of high-molecular Almazov by HPLC on many speakers

Excellent way of separating high molecular Almazov with a high degree of purity is the use of HPLC in two or more the number of consecutive columns with different selectivity.

First, the HPLC system consisted of two sequential octadecylsilane (ODS) columns Whatman M20 10/50, in which as mobile phase was used acetone with a flow rate of 5.00 ml / min. He was selected series of fractions obtained by HPLC (Fig. 32). Faction # 36 and # 37 were combined and taken for further purification on a second HPLC system. This combined fraction (#36 and # 37) contained exemestane No. 7, No. 11 and No. 13 (Fig. 32, and Fig. 35B).

Further purification of these combined fractions obtained by HPLC on an ODS column was performed using the HPLC column type Hypercarb stationary phase, to ora had different selectivity in the allocation of different exemestane, than the above ODS column. In Fig. 33 shows the values of time of elution of the individual exemestane on the column for HPLC type Hypercarb (with acetone as mobile phase).

By comparing these two drawings of Fig. 32 and Fig. 33 visible differences in elution time and in the sequence of elution of exemestane when HPLC on an ODS column and column type Hypercarb. For example, elution of exemestane No. 11 and No. 13 in the system HPLC on ODS column occurs simultaneously (Fig. 32), but in the system with column type Hypercarb their elution occurs in a separate fractions (respectively, fraction No. 32 and fraction No. 27) (Fig. 33).

The presence of different sequences of elution and different time of elution of the selected high molecular Almazov in these two systems can be used to separate high molecular Almazov, elution occurs together. It can also be used to remove impurities. Using this method for the combined fractions No. 36 and No. 37, obtained by HPLC on an ODS column, was the selection of appropriate fractions obtained by HPLC on a column of type Hypercarb, due to what we obtained exemestane No. 13 (Fig. 33) with a high degree of purity. Other borders separating distillation by HPLC on an ODS column and what exploits HPLC on a column of type Hypercarb can be used to highlight other examintaion. This concept of the selection of components is also applicable for the separation of other macromolecular Almazov despite the fact that the compositions of the solvents for elution may vary.

In these processes the selection of the UDF column and the column type Hypercarb can also be used in reverse order. By using a methodology similar to the above, i.e. by dividing the fractions obtained on ODS column, into smaller fractions containing hexameter, using column type Hypercarb or other suitable column, and collect them in the time of elution can be carried out selection of the rest of exemestane with a high degree of purity. This is also true for other high-molecular Almazov from tetramantane to undocumented, including their substituted forms.

EXAMPLE 2

Repeated steps 1, 2, 3, 4, 5 and 6 of example 1 (Fig. 34). Then the operation was performed 7 in the following amended form.

Operation 7'

To highlight exemestane from the reaction product obtained by operation 6 of example 1, was used preparative capillary gas chromatograph with two columns. The times of sampling fractions exemestane on the first preparative capillary GC column, the equivalent column DB-1 on methylsilicone, b is set using the values of the retention time and diagrams obtained by gas chromatography/mass spectrometry (GC/MS) analysis. (step 2 of example 1). The results are shown in Fig. 37A, were selected two fractions, referred to as "fractions corresponding to the peaks that are selected and transferred to the second column, which contain two components, representing hexameter isolated from the source of reagent B.

The first column was used to increase the concentration of high molecular weight Almazov, such as exemestane, by taking fractions, which were then sent to the second column (Fig. B, where the data for exemestane # 2 and # 8). By the second column on phenyl-methylsilicone equivalent to DB-17, was carried out a further separation and purification of exemestane, which were then used to allocate fractions of the relevant interest the highs, and store them in separate traps (traps 1-6). Fraction No. 1, collected in gas chromatography (GC) the trap contains crystals exemestane No. 2. Fraction No. 3, collected in the GC trap, contains crystals of exemestane No. 8. Subsequent gas chromatography/mass spectrometry (GC/MS) analysis of substances contained in the trap No. 1, showed that it is hexameter No. 2 high purity, based on rezultatov/MS analysis of the sample according to operation 2. Similarly, GC/MS analysis of substances contained in the trap No. 3, showed that it represents, basically, hexameter No. 8 (Fig. 28B and Fig. 28V). Both exemestane No. 2 and No. 8 (Fig. 28A) formed crystals. To highlight other exemestane this procedure could be repeated. This procedure is also applicable for the selection of other high-molecular Almazov.

EXAMPLE 3

Repeated steps 1, 2, 3, and 4 (Fig. 34) example 1 using the source reagent A. the residual fraction from the distillation of the source reagent at atmospheric pressure, extracted at operation 4, has a very low concentration of components that are not almatadema. The pyrolysis operation (operation 5) of example 1 may be omitted, especially in the case when the target high-molecular almatadema are tetramantane, pansamantala and cyclohexanone. In this case, the fraction removed at operation 4, pass directly to the operations 6 and 7 of example 1 or directly to the step 7 of example 2 (Fig. 34). This modified process can also be applied for fractions of the original reagent B containing tetramantane with a lower boiling point. However, the operation of the pyrolysis is very desirable in the presence of high content of components that are not almatadema.

From this source the first reagent was selected fraction, boundary separation which distillation corresponds to the fraction No. 1 of operation 4 (see Protocol distillation from table 3, example 1 and Fig. 12). Performed additional fractionation of this fraction by preparative capillary gas chromatography in a manner analogous to the method of processing transactions 7' from example 2 (Fig. 34).

Was then used preparative capillary gas chromatograph with two columns for the separation of target tetramantane from the fraction distillation, purified by the method chromatography on columns (6, Fig. 34). Using the values of the retention time and diagrams, obtained by GC/MS analysis of samples (in the result of the operation 2, example 1), were specified time value of separating fractions containing the target alasoini (for example, tetramantane), for the first preparative capillary GC columns on methylsilicone equivalent to DB-1. The results are shown in Fig. 6A and shown as fractions 1, 2 and 3.

The first column was used to increase the concentration of the target Almazov (for example, tetramantane) by taking fractions, which were then allocated to the second column (phenyl-methylsilicone, equivalent DB-17) (Fig. 6B). By the second column was provided with additional separation and purification of target Almazov, which were then directed the trading in individual traps (traps 1-6). GC traps 2, 4 and 6 contain the selected tetramantane (Fig. 6B).

Then have the possibility of crystallization of Almazov having a high concentration in the trap or from a solution. When observed under a microscope at 30-fold increase in preparative fractions collected in the GC traps 2, 4, and 6 (Fig. 6), were visible crystals. When the concentrations were not high enough to cause crystallization, needed more concentration by preparative GC. Patterns of isomers tetramantane shown in Fig. 7, with one [123] tetramantane using item Balaban (reference 15), in two enantiomeric forms. In Fig. 8A, Fig. 8B and Fig. 8B shows a micrograph of crystals of tetramantane, selected respectively from fraction No. 2, fraction # 4 fraction No. 6 original reagent And collected in preparative GC the interceptor.

After obtaining crystals of appropriate size substance may be sent to determine its structure by x-ray diffraction.

The results of GC/MS analysis (Fig. 9) indicate a possible presence in the faction No. 38 distillation target Almazov, heavier than tetramantane (pentimento and exemestane). In addition, the results of GC/MS analysis of fraction No. 38 (source reagent A) indicate in n the th garamantes (Fig. 10 and Fig. 11).

EXAMPLE 4

Preparative GC fractions obtained by HPLC

To obtain garamantes, artamanov, other high molecular Almazov, etc. may be desirable to perform additional separation into fractions of the products obtained by HPLC in the result of the operation 7 of example 1. This can be accomplished using the method of preparative capillary gas chromatography according to operation 7' of example 2.

EXAMPLE 5

Pyrolysis fractions No. 5 of the distillation of the source reagent B

For purification of fraction No. 5 distillation, obtained by distillation of the source reagent B at atmospheric pressure and a temperature of 650°F + residues (tables 3A and 3B, Fig. 12 and Fig. 31), was used the method 5 of example 1, the operation in which use high thermal stability of hydrocarbons, representing high alasoini, in relation to other components of crude oil. In Fig. 13 shows gaschromatograph fraction No. 5 distillation, obtained by distillation of the source reagent B at atmospheric pressure and a temperature of 650°F + residues (Fig. 12 and tables 3A and 3B). Shown in Fig 14, the ion chromatogram obtained by GC/MS analysis shows the presence of this fraction No. 5 distillation target garamantes.

Was conducted pyrolysis fractions No. 5 p and a temperature of 450° C in the course of 16.7 hours according to the procedure of example 1, the operation 5. In Fig. 21 shows the result of this process and shows a gas chromatogram (GC column, equivalent to DB-17) the parent substance of Fig. 21 (shown in the upper part of the drawing) and the product of pyrolysis of Fig. 21 (shown in the lower part of the drawing).

In Fig. 22 in an enlarged scale shows the time interval from GC 28,2 min up to 31.5 min, indicating the presence of exemestane and heptamethine. This product of pyrolysis was used in example A.

EXAMPLE 6

Removing components that are not almatadema using pyrolysis in the allocation of tetramantane

Was repeated example 1 were changed conditions of operation 5. In this way for the implementation of pyrolysis and decomposition of part of the components that are not almatadema was used high-temperature reactor, whereby it was provided enrichment remainder almatadema. The explanation of this method is shown in Fig. 15 and Fig. 16, which shows the gas chromatogram of the product before pyrolysis (for example, in Fig. 15) and the product obtained by pyrolysis (for example, in Fig. 16).

For processing substances, detainee distillation column after distillation of the source reagent at atmospheric pressure, was used reactor PARR® byPARR INSTRUMENT COMPANY, Moline, llinois . In this example as a starting reagent for pyrolysis was used by the product of the distillation of the source reagent B at a temperature of 650 °F + retention column distillation. This was followed by pyrolysis of this sample by heating the sample in a vessel under vacuum at a temperature of 450°C for 20,4 hours.

In Fig. 15 shows a gas chromatogram of a substance, the detainee distillation column, and Fig. 16 shows a chromatogram of the products of the pyrolysis process. The Comparison Of Fig. 15 and Fig. 16 shows that as a result of the pyrolysis process was ensured removal of a major part of the components that are not almatadema, and was provided with enrichment of the residue by almatadema, mainly tetramantane.

EXAMPLE 7

The selection of tetramantane using HPLC

It was also demonstrated that in addition to the above-described method of pyrolysis sufficient enrichment of some high-molecular almatadema, enabling them to crystallization without pyrolysis can be carried out by HPLC. In some cases, this treatment can be carried out by HPLC reverse phase with acetone as mobile phase. Was made a run fraction No. 32 distillation of the source reagent And representing the condensate via preparative HPLC, and was registered items is metagrammar, obtained by HPLC using a differential Refractometer, which is shown in Fig. 17. During the run, we selected nine fractions, shown in Fig. 17. As columns for HPLC were used two sequential octadecylsilane (ODS) column type Vydac internal dimensions 25 cm x 10 mm (Vydac column manufactured byThe Separatations Group, Inc., CA, USA). In the column was introduced sample volume of 20 microliters, representing a solution of fraction No. 32 in acetone with a concentration of 55 mg/ml Columns were adjusted so that the amount of acetone used as the mobile phase, was 2,00 ml per minute.

In Fig. 36 shows a different sequence of elution of tetramantane when HPLC on ODS columns and for columns of type Hypercarb, indicating how it can be implemented sharing of columns of these two types to select tetramantane (and pentimento) with a high degree of purity.

In Fig. 18 shows the comparison of gas chromatograms of the original substance (fraction No. 32 distillation of the source reagent a) and fraction No. 6 of Fig. 17, obtained by HPLC. Fraction No. 6, obtained by HPLC, significantly enriched tetramantane (see results of GC/MS analysis is shown in Fig. 19), and its concentration close to the concentration that t is aetsa sufficient in order to cause crystallization.

EXAMPLE 8

Comparison of initial reagents and procedures for the selection

This example illustrates the extraction procedure, through which increase the concentration of high molecular weight Almazov in different source reagents for their subsequent separation.

Table 5 shows the concentrations of high molecular weight Almazov in the selected condensates having a high concentration of Almazov, compared with concentrations of high-molecular Almazov contained in conventional oil. The condensates produced from the reservoir Norfleet (Norphlet), the Northern part of the Gulf coast, and from the reservoir LeDuc (LeDuc) in Canada, have a high initial concentration of Almazov, including high-molecular Almazov. A typical crude oil usually contains adamantanes, the concentration of which is approximately 200-400 ppm (part per million). The content of high-molecular Almazov is approximately 0.5 wt.% from the total mass of Almazov in a typical crude oil.

Table 5
Comparison of concentrations of high-molecular Almazov contained in conventional oil, with their concentration in the selected condensates, enriched amazoid and
The original substanceThe concentration of high molecular weight Almazov (tetramantane and more high-molecular compounds)
Conventional oil1 ppm or less
Selected natural gas liquids enriched with almatadema2500 ppm

Can also be found and other suitable source reagents in the flow of products of processing of crude oil. The concentration of high molecular weight Almazov in each thread processing products depends on the type of crude oil and refining operations, including borders separating distillation, from used catalysts or other processing operations (e.g., coking), which can lead to an increase in the concentration of high molecular weight Almazov. These flows of oil products subjected to additional processing, are potential raw material for extraction of high-molecular Almazov.

Table 6 shows evidence about the increase in the concentration of high molecular weight Almazov in the primary procedures discharge materials from the source reagent. Such allocations can be distilled at atmospheric pressure, vacuum distillation, contact degassing or other methods of separation, reinforcement of the local experts in this field of technology. In addition, this product is subjected to processing, can be further subjected to another separation process, such as pyrolytic processing, which combine with the first process.

Table 6
Comparison of selected procedures initial allocation used to allocate Almazov from conventional oil and condensate enriched almatadema
Procedures for the primary allocation used for fractions containing high molecular weight alasoiniThe concentration of high-molecular Almazov (conventional oil)The concentration of high-molecular Almazov (condensate)
Distillation at atmospheric pressure1 ppm to 100 ppm> 95 wt.%
Distillation at atmospheric pressure, pyrolytic processing and allocation of saturated hydrocarbons by liquid chromatography> 50 wt.%> 50 wt.%

The measured concentration values listed in Table 6, depend on the weight percent of the residue of the distillation at atmospheric pressure (the residue after distillation at atmospheric pressure and a temperature of 650°F (345°C)). In the residue from the distillation of crude oil at uspernom pressure are high alasoini, and the weight percent of the residue from the distillation of crude oil at atmospheric pressure can vary from approximately 1% to less than about 80 wt.%.

Although Table 6 shows data for a combination of operations of distillation at atmospheric pressure and pyrolytic treatment, pyrolytic treatment (thermal decomposition of substances, which are not almatadema) may be subjected source reagent, is not subjected to distillation, or fraction by vacuum distillation. In this case, the source reagent is subjected to pyrolytic processing may be subsequently subjected to the operation of removal of low molecular weight Almazov.

Secondary allocation may include either vacuum distillation or vacuum distillation in combination with liquid chromatography.

Before pyrolytic processing can be also performed the separation of residue from distillation at atmospheric pressure to a fraction.

Between fractions isolated through distillation, there is a slight overlap of the rows of high-molecular Almazov, such as a distillation of the most structurally Packed isomer of exemestane occurs at lower temperatures than other exemestane, and find in the distillation fractions containing pentameter. Similarly, the distillation of the most densely Packed is somerow number of heptamethine occurs with exemestane, having not maximally Packed structure, etc. in Addition, because each subsequent series of high-molecular Almazov the number of isomers with different molecular weight increases, it increases the range of the boiling points of the substances in this series and their isomers, with the increase in molecular weight occurs gradually increasing the overlap of the series. In addition, the presence of isomers of substitute groups also affects the fraction distillation.

For additional purification of the products obtained in the second extraction procedure can be used tertiary allotment, or it can be used instead of a secondary procedure. For example, can be carried out the removal of aromatic hydrocarbons using liquid chromatography.

Tertiary extraction procedure shall be implemented by, for example, preparative gas chromatography and high performance liquid chromatography. Specialists in this field known in the art, other suitable methods of separation. Through these tertiary procedures selection receive the mixture from which the individual connections can be usually, but not always, crystallized for allocation. In Table 7, the highest values of purity suggests vozmozhnostzanimatsya. Substances with a much higher degree of purity can be obtained by techniques such as zone refining and vacuum sublimation.

Table 7
The degree of purity of individual macromolecular Almazov obtained through tertiary procedures of selection
Tertiary procedures for isolating individual fractions containing tetramantane, pentamadine, exemestane etc.The degree of purity of Tetra-montanovThe degree of purity of the Penta-montanovThe degree of purity hexa-montanovThe degree of purity hepta-montanovThe degree of purity of Oct-montanovThe degree of purity Nona-montanovThe degree of purity DECA-montanov
Preparative gas chromatography>to 99.9>to 99.9>to 99.9>to 99.9>to 99.9>to 99.9>to 99.9
High performance liquid chromatography high-resolution>30-99,9>20-99,9>10-99,9>5-99,9>2-99,9>1-99,9>1-99,9

EXAMPLE 9

The selection of pentimento by preparative capillariasis chromatography

In order to demonstrate the selection process pansamantala, fraction distillation containing pansamantala was processed using preparative capillary gas chromatography.

There was obtained a fraction No. 38 refining by distillation of the source reagent And representing the condensate, and processed using liquid chromatography (on silica gel containing 10% silver nitrate) removal of all substances, except saturated hydrocarbons (Fig. 34). Collection of fractions preparative gas chromatograph was adjusted to provide for the collection of a substance corresponding to the maximum (peak), identified as the isomer pansamantala by gas chromatography/mass spectrometry (GC/MS) analysis (step 2, Fig. 34,).

To ensure allocation of pansamantala was used preparative gas chromatograph with two capillary columns. The sample fraction distillation in cyclohexane solution was introduced (1 microliter) in the first gas chromatography column, while it is operated in the mode without divider in the intake hole. The sample was separated into fractions using (non-polar) gas chromatographic column, and the fraction corresponding to the maximum chromatogram for the search pansamantala,was allotted to the second (polar) chromatographic column for further separation of target pansamantala. A substance designated in the second column, was further subjected to separation into fractions, and thus ensured the capture of the two selected pentimento in the form of a reaction product sent in the collection of fractions.

Preparative gas chromatograph was equipped and able to operate in an automated mode.

Once in the collection trap was collected a sufficient number of allocated pansamantala, the trap was removed from the chromatograph, these two pansamantala were dissolved in cyclohexane, and was made their crystallization. In Fig. 23 shows the crystal with a diameter of approximately 250 microns, which was dissolved in cyclohexane and subjected to recrystallization. It consists of two cocrystallization of pentimento. This procedure was also subjected to a pyrolysis product from example 5 (purified using step 5 of example 1) to highlight pansamantala No. 1 (first pentameter for elution in GC/MS analysis). In Fig. 27 shows a micrograph of crystals of pansamantala No. 1, and Fig. B and Fig. 27B shows the total ion chromatogram current (PETE)obtained by GC/MS analysis, and mass spectrum, indicating the high purity substances selected using this procedure.

EXAMPLE 10

The presence of garamantes, is Tarantino and Diamantino in the products of pyrolysis

Ion chromatogram shown in Fig. 24, Fig. 25 and Fig. 26 indicate the presence of these high-molecular Almazov in the treated product of the pyrolysis of example 1 operation 6. In particular, in Fig. 24 shows the chromatogram is not maximally Packed heptamethine with respect to m/z equal to 448 of Fig. 25 shows the chromatogram maximally Packed artamanov with respect to m/z equal to 446 of Fig. 26 shows the chromatogram maximally Packed diamantane with respect to m/z equal to 456. Data gas chromatography/mass spectrometry (GC/MS) analysis, shown on these drawings were used as data GC/MS analysis (step 2 of example 1) of the samples in examples 11, 12 and 14.

EXAMPLE 11A

The separation of the components constituting garamantian by preparative capillary gas chromatography

Eluent obtained by chromatography on columns (6, Fig. 34), was subjected to gas chromatography/mass spectrometry (GC/MS) analysis to determine the retention time of heptamethine at GC. The individual components of heptamethine with a molecular mass equal to 394 and 448, were assigned numbers in the order of their elution in a given sample, subjected to GC/MS analysis (Fig. 35A, which presents the results of the analysis). For convenience, this is m example were selected heptamethine with molecular weight, equal 448, with the highest relative content of all substances collection garamantes. A similar analysis could be performed for heptamethine with different molecular weight.

Then there was carried out the selection of heptamethine of distillation fractions subjected to the purification method chromatography on columns, which was implemented by preparative capillary gas chromatograph with two columns. Time values corresponding to the boundaries of the sampling fractions containing heptamethine, for the first preparative capillary gas chromatography column, equivalent to DB-1 on methylsilicone were defined using the values of the retention time and diagrams obtained from GC/MS analysis of samples (as a result of the above operation 2, Fig. 34).

The first column was used to increase the concentration of heptamethine by taking fractions, which were then sent to the second column. By the second column on phenyl-methylsilicone equivalent to DB-17, was carried out a further separation and purification of components representing garamantian, which were then used to allocate fractions of the relevant interest the highs, and store them in separate containers (traps 1-6). Fraction No. 2, collected in gas chromatography (GC) St is the representative, was subjected to further processing to highlight heptamethine No. 1. Fraction No. 4, collected in the GC trap, was subjected to further processing to highlight heptamethine No. 2. Subsequent gas chromatography/mass spectrometry (GC/MS) analysis of substances contained in the trap No. 2 (Fig. 29B and Fig. 29B), showed that it is garamantian No. 1, on the basis of previously obtained results of GC/MS analysis of samples when they are run at the stage of operation 4. Similarly, GC/MS analysis of substances contained in the trap No. 4, showed that it is garamantian No. 2. For the selection of other components, representing garamantian, this procedure could be repeated.

Then have the possibility of crystallization of heptamethine having a high concentration, or directly in the trap or from a solution. In preparative fractions collected in the GC trap No. 2, with its observation under a microscope with 30x magnification were visible crystals (Fig. 29A). These crystals were transparent and had a high refractive index. To highlight the component that represents garamantian No. 1, never existed in crystalline form. In those cases, when the concentration is high enough to ensure crystallization may be necessary the additional concentration by preparative GC. To highlight the component that represents garamantian No. 2, never existed in crystalline form.

After obtaining crystals of appropriate size substance representing garamantian, can be transferred for analysis of their structure by x-ray diffraction. The enantiomeric heptamethine can be subjected to additional separation for separation of these two components.

EXAMPLE 11B

Cleaning components that contain only garamantian by HPLC

It was also demonstrated that by means of HPLC can be carried out enrichment of some heptamethine to a degree sufficient to ensure their crystallization.

As columns for HPLC were used the same column, in other examples (ODS column and column type Hypercarb). In the ODS column was introduced sample volume of 500 microliters, representing a solution of the product of pyrolysis fractions No. 7 containing saturated hydrocarbons (product received at operation 6, Fig. 34). Pyrolysis was used to 25.8 g of fraction No. 7, which was heated at a temperature of 450°C for 16 hours. For some of the fractions obtained by HPLC on an ODS column was provided with a degree of purity required for crystallization of the individual garamantes (e.g., fraction No. 45, the scientists by HPLC on ODS columns). For other factions, for example, for a fraction No. 41, obtained by HPLC on ODS columns, which contains garamantian No. 2, for a fraction No. 61, obtained by HPLC on ODS columns, which contains garamantian No. 9, for the fraction No. 87, obtained by HPLC on ODS columns, which contains garamantian No. 10, need for more separation on the HPLC systems with different selectivity. By run fractions (Fig. 35B), received by ODS column through the column type Hypercarb we obtained separate components representing garamantian, with the degree of purity required for crystallization, as demonstrated for the component representing garamantian No. 1 contained in fraction No. 55, obtained by HPLC on a column of type Hypercarb, as well as for the component representing garamantian No. 2. High alasoini contained in the various fractions obtained by HPLC, could be separated with the use of additional methods of chromatographic separation, including by preparative gas chromatography and additional runs in the system HPLC using columns with different selectivity, as indicated below. In addition, for cleaning heptamethine could be used and other methods known in the region of the crystallization, including sublimation fractions, serial recrystallization or band treatment, but these examples are not restrictive.

Selection of the rest of heptamethine can be carried out using a technique similar to the above, i.e. by dividing the fractions containing garamantian obtained by ODS column, into smaller fractions using column type Hypercarb or other suitable column, and collect them in the time of elution. It is also true that in the original reagents used by the authors of the present invention, the relative content of heptamethine having a molecular weight of 420 and 434, is much lower than the component representing garamantian, with molecular weight of 394 and 448. In fraction No. 61, highlighted by a run through the system HPLC on ODS column, in the mass spectrum of the component with respect to m/z equal to 420, and the corresponding point in time, equal 16,71 min, detected the presence of a very strong molecular ion component, representing garamantian with a molecular weight of 420.

EXAMPLE 11B

Selection substituted heptamethine

In the original reagents a and B also contain substituted heptamethine, including alkylhalogenide. Cleaning alkylhalogenide can be done is by removal of the initial reagents, impurities, non-almatadema through the pyrolysis process described above. After the pyrolytic processing remain some alkylhalogenide, as well as the above components, representing heptamethine. Substituted heptamethine, including alkylhalogenide, can be selected with a high degree of purity using a single separation by HPLC. Monomethylamine heptamethine have a molecular mass equal to 408 (resulting in mass spectrometric analysis receive a molecular ion with respect to m/z equal to 408), and the loss of a methyl group at mass spectrometric analysis leads to the presence of the fragment ion subjected to mass spectrometric analysis, with the ratio of m/z equal to 393, indicating that this component heptamethine.

EXAMPLE 12A

The separation of the components constituting octameter

Enriched with octameter fraction resulting from operation 6 was subjected to separation by HPLC reverse phase. In some cases, to provide such treatment can be used HPLC reverse phase with acetone as mobile phase. Was made to run pyrolysis product fractions No. 7, isolated by distillation of the source reagent B containing saturated hydrocarbons, through a system of preparation is effective HPLC on ODS columns, and was registered chromatogram separation by HPLC using a differential Refractometer. Was performed by gas chromatography/mass spectrometry (GC/MS) analysis of the fractions obtained by HPLC, to determine the values of time of elution of otamatone when HPLC and control its purity (Fig. 35A, where the results of analysis of samples). For this HPLC system was used the same ODS column (Fig. 35B) and column type Hypercarb, as in the previous examples. In the ODS column was introduced sample volume of 500 microliters, representing a solution of the product of pyrolysis (25 mg) of fraction No. 7 containing saturated hydrocarbons in acetone. Despite the use of this system HPLC were obtained some otamatone purity, sufficient to provide crystallization of individual artamanov. Fraction No. 63, selected by HPLC, contained a set of components representing octameter No. 3 and octameter No. 5, crystallization of fraction occurred together.

For the selection of other components, representing octameter, with a high degree of purity can be used a variety of speakers, for example Hypercarb.

EXAMPLE 12B

The separation of the components constituting the substituted otamatone

Cleaning alkylation what new can be done via the above methods, used to highlight dealkilirovanny of artamanov. Fraction No. 94, obtained by HPLC on ODS columns, contains methylated octameter with a high degree of purity. Monomethylamine otamatone have a molecular mass equal to 460 (resulting in mass spectrometric analysis receive a molecular ion with respect to m/z equal to 460), and the loss of a methyl group at mass spectrometric analysis leads to the presence of the fragment ion subjected to mass spectrometric analysis, with the ratio of m/z equal to 445, indicating the presence of component otamatone. Moreover, in the case when the fraction obtained by HPLC on an ODS column or column type Hypercarb, contains more than one alkylacrylate, obtaining high-purity alkylacrylate can be provided by additional separation of the fractions by HPLC or by means of the procedure of preparative GC (as in example 3).

EXAMPLE 13A

The separation of the components constituting monumental

Was made to run pyrolysis product fractions No. 7, isolated by distillation of the source reagent B containing saturated hydrocarbons through preparative HPLC on an ODS column and fractions obtained by HPLC were subjected to gas chromatography/mass spectrometry (GC/MS) EN the lease to determine the values of time of elution of nanananana when HPLC and control its purity. In the column was introduced sample volume of 500 microliters, representing a solution of the product of pyrolysis (25 mg) of fraction No. 7 containing saturated hydrocarbons, acetone. Columns were adjusted so that the amount of acetone used as the carrier of the mobile phase was to 5.00 ml / min.

To highlight nanananana (Fig. 38) can be used method HPLC on multiple columns. For an explanation of this technique was carried out highlighting only nanananana by HPLC on consecutive columns with different selectivity (ODS column and column type Hypercarb described in the previous examples). Fraction No. 84-No. 88 (Fig. 35B), highlighted by a run through the system HPLC on ODS columns and containing monumental, were combined for further purification in the system HPLC on columns of type Hypercarb.

The sample volume of 50 microlitres, representing a solution of the combined fractions (fractions No. 84-No. 88), obtained by HPLC on ODS columns, weighing approximately 1 mg in methylene chloride, was introduced in two columns of type Hypercarb (having an inner diameter of 4.6 mm and height 200 mm)operating consistently with the use of methylene chloride with a flow rate of 1.30 ml / min as mobile phase.

Monumental was selected in the third run through the system HPLC using the same column type is Hypercarb stationary phase, but the solvent consisted of a mixture of methylene chloride and acetone (volume percentage was 70:30, and work flow was equal to 1.00 ml per minute).

By using a technique similar to that described above, i.e. the separation of the fractions obtained by HPLC on ODS columns and containing monumental, into smaller fractions by using columns with different selectivity, such as column type Hypercarb or other suitable columns was carried out highlighting nanananana having a molecular weight equal to 498, with a high degree of purity (Fig. 39 and Fig. 40). This method could be repeated to highlight nanananana with a molecular mass equal to 552, and nonlatino with a molecular mass equal to 538, 484 and 444, the relative contents of which are used in the source reagent is correspondingly lower. It should be noted that the enantiomeric nonmonetary can not be separated by gas chromatography/mass spectrometry (GC/MS) analysis, however, these enantiomers can be separated by means of separation of chirality.

EXAMPLE 13B

Selection substituted nanananana

In the original reagents a and B also contain substituted nonmonetary, including alkeneamine. Cleaning alkylresorcinol can be carried out via the above methods, which is used to highlight dealkilirovanny of nonlatinos. One kind monomethylamine of nanananana has a molecular mass equal to 512 (resulting in mass spectrometric analysis receive a molecular ion with respect to m/z 512), and the loss of a methyl group at mass spectrometric analysis leads to the presence of the fragment ion subjected to mass spectrometric analysis, with the ratio of m/z 497, indicating the presence of component nanananana. Fractions containing more than one alkylenediamine, and their allocation to obtain alkylresorcinol with a high degree of purity could be achieved by further separation by HPLC or preparative GC using ODS column or columns type Hypercarb.

EXAMPLE 14A

The separation of the components constituting Diamanten

Was made to run pyrolysis product fractions No. 7, isolated by distillation of the source reagent B containing saturated hydrocarbons through preparative HPLC on an ODS column and fractions obtained by HPLC were subjected to gas chromatography/mass spectrometry (GC/MS) analysis to determine the values of time of elution of diamantane when HPLC and control its purity. As columns for HPLC were used two octadecylsilane (ODS) column Whatman internal dimensions 50 cm × 20 mm, rabotaushi the series. In the column was introduced sample volume of 500 microliters, representing a solution of the product of pyrolysis (25 mg) of fraction No. 7 containing saturated hydrocarbons, acetone. Columns were adjusted so that the amount of acetone used as the carrier of the mobile phase was to 5.00 ml / min.

To select a component, representing Diamanten, can be used a method HPLC on multiple columns. For an explanation of this technique was carried out highlighting only diamantane by HPLC on consecutive columns with different selectivity. First, the HPLC system consisted of the above ODS columns. Fraction No. 74 No. 83, highlighted by a run through the HPLC system containing Diamanten, were combined for further purification in the second HPLC system. Was performed five such runs, and all highlighted in the result of these runs the fractions containing Diamanten, were combined. This combined fraction contained documenten with a molecular mass equal to 456, and various impurities.

For treatment of combined fractions No. 74 No. 83, obtained by HPLC method for the separation by HPLC on ODS columns, the sample volume of 50 microlitres, representing a solution of the combined fractions obtained by HPLC on ODS columns, weighing approximately 1 mg in acetone/m is telecharge (volume percentage 70:30) was introduced into the two working consistently column type Hypercarb, having an internal diameter of 4.6 mm and a height of 200 mm, where as the mobile phase at a pressure of 480 psi) was used a mixture of acetone and methylene chloride (volume percentage 70:30) with a flow rate of 1.00 ml / min, and selection was carried out (Fig. 39) diamantane and its crystallization (Fig. 40).

By using a technique similar to that described above, i.e. the separation of the fractions obtained by HPLC on ODS columns and containing Diamanten, into smaller fractions by using columns with different selectivity, such as column type Hypercarb or other suitable columns was carried out highlighting Diamantina having a molecular weight equal to 456, with a high degree of purity (Fig. 39 and Fig. 40). This method could be repeated to highlight Diamantino with a molecular mass equal to 496, and with a molecular mass equal to 550 or 604, and Diamantino with molecular weight, 536, 576 and 590, the relative contents of which are used in the source reagent is correspondingly lower. It should be noted that the enantiomeric documentary can not be separated by gas chromatography/mass spectrometry (GC/MS) analysis, however, these enantiomers can be separated by means of separation of chirality.

EXAMPLE 14B

Selection someseni is Diamantino

In the original reagents a and B also contain substituted documentary, including alkyladamantanes. Cleaning alkyladamantanes can be carried out via the above methods, which were used to extract dealkilirovanny of Diamantino. One kind monomethylamine of diamantane has a molecular mass equal to 470 (resulting in mass spectrometric analysis receive a molecular ion with respect to m/z equal to 470). Moreover, in those cases when the fraction obtained by HPLC on an ODS column or column type Hypercarb, contains more than one alkyladamantanes, this fraction may be subjected to additional separation by HPLC or, alternatively, by means of the procedure of preparative GC, which gives alkyladamantanes with a high degree of purity.

EXAMPLE 15

The separation of the components constituting undocumented

To select a component, representing undocumented with a high degree of purity, can be used a method HPLC on multiple columns. To explain this technique to highlight a single undecalactone was used HPLC on consecutive columns with different selectivity. As the corresponding original substance was used pyrolysis product fractions No. 7, support the military by distillation of the source reagent B.

A high concentration of undocumented had a fraction No. 100+, obtained by HPLC on ODS columns (Fig. 35B). This fraction can be subjected to purification using HPLC system on columns of type Hypercarb, similar to the above system, which was used to highlight Diamantina. This method could be repeated to highlight undocumented with a molecular mass equal to 656 and/or 602, and also undocumented with a molecular mass equal to 642 628, 588, 548, or 534, which, as expected, have, respectively, a lower relative content in the original reagents used.

1. The method of extraction of the composition of the original hydrocarbon enriched components representing tetramantane, and components representing other high alasoini, including the following:

a) selecting a source reagent containing components representing tetramantane, and components representing other high alasoini, in the amount recoverable;

b) removing from the source reagent sufficient amount of components having a boiling point less than the lowest boiling point component, representing tetramantane, the conditions under which the components representing subiterator, and components representing other high alasoini remain in the treated source reagent in the amount recoverable; and

C) heat treatment of the source reagent extracted in the operation (b), pyrolysis, at least, a sufficient number of contained components that are not almatadema to extract components representing tetramantane, and components representing other high alasoini, from the source reagent subjected eroticheskoe processing, with the specified pyrolysis is carried out in conditions which ensure the preservation of the processed source reagent components representing tetramantane, and components representing other high alasoini, in the amount recoverable.

2. The method according to claim 1, wherein the source reagent additionally contains components that are not almatadema, having a boiling point both below and higher than the lowest boiling point component, representing tetramantane, and at least one component representing low-molecular almasoud.

3. Means for retrieving, enriched components representing tetramantane, and components representing other professional who colerne alasoini, includes the following operations:

a) selecting a source reagent containing components representing tetramantane, and components representing other high alasoini, in the amount recoverable;

b) heat treatment of the source reagent for pyrolysis, at least, a sufficient number of contained components that are not almatadema to extract components representing tetramantane, and components representing other high alasoini, from the source reagent is subjected to pyrolytic processing, with the specified pyrolysis is carried out in conditions which ensure the preservation of the processed source reagent components representing tetramantane, and components representing other high alasoini, in the amount recoverable; and

C) removing from the source reagent sufficient number of those remaining after pyrolysis of components that have a boiling point less than the lowest boiling point component, representing tetramantane, in conditions which ensure the preservation of the processed source reagent components representing tetramantane, and components representing other macromolecular shall lasode, in the amount recoverable.

4. The method according to claim 1 or 3, in which the source reagent removed a sufficient number of components representing a low-molecular alasoini, to ensure that the ratio of the number of components representing a low-molecular alasoini, the number of components constituting the high-molecular alasoini, processed in the source reagent is about 9:1 or less, 2:1 or less, or 1:1 or less.

5. The method according to claims 1 to 4, in which the source reagent after the operation (b) is at least about 10% or at least about 50% of the specified components, representing tetramantane, and components representing other high alasoini, compared with the quantities of these components are present before the specified operation.

6. The method according to claim 1 or 3, wherein the source reagent remains after pyrolysis of at least about 10% or at least about 50% of the specified components, representing tetramantane, and components representing other high alasoini, compared with the number before pyrolysis.

7. The method according to claim 1 or 3, wherein the delete operation from the source reagent components that are not almatadema, and/or components are presented in the shining a low-molecular alasoini, includes the operation of the distillation of the specified source reagent.

8. The method according to claim 7, in which the removed components representing a low-molecular alasoini, in the amount of at least about 50% of the total weight of components representing a low-molecular alasoini contained in the raw source code.

9. The method according to claim 1 or 3 which further includes removing from the product obtained in operation (b)components representing tetramantane, and components representing other high alasoini, by applying one or more separation methods selected from the group consisting of chromatographic methods, methods based on thermal diffusion, crystallization, sublimation and means separation by size, including liquid chromatography, gas chromatography and high performance liquid chromatography.

10. The method according to claim 1 or 3, wherein the product obtained in operation (b), contains deionized components representing tetramantane, and components representing other high alasoini, in the amount of at least 10 wt.% and ionized components representing pentameter, and components representing other high alasoini, in quantity, less than the least 0.5% relative to the total weight of all components present, representing alasoini.

11. The method according to claim 1 or 3, wherein the product obtained in operation (b), contains deionized components representing tetramantane, and components representing other high alasoini, in the amount of at least 10 wt.% and ionized components representing pentameter, and components representing other high alasoini, in the amount of at least 0.5% relative to the total weight of the extracted source reagent.

12. The composition of the enriched components representing tetramantane, and components representing other high alasoini obtained by the method according to claim 1 or 3, containing at least the components representing tetramantane, and pentameter, and the composition contains components representing tetramantane, in the amount of at least about 10 wt.% and components, representing pentameter, in the amount of at least 0.5% relative to the total weight of all components present, representing alasoini.

13. The composition according to item 12, containing components representing tetramantane, in the amount of at least about 25%, components, represents the existing pentameter, in the amount of at least 0.5 percent relative to the total weight of the composition.

14. The method of obtaining the composition of the original hydrocarbon containing recoverable amounts of high-molecular almasoud, including

a) selecting a source reagent containing selected to extract the component or components constituting the high-molecular alasoini, in the amount recoverable, the components that are not almatadema, and components representing alasoini, having a boiling point lower than the lowest boiling point selected for retrieval component, which represents the high-molecular almasoud;

b) removing from the source reagent sufficient amount of components having a boiling point less than the lowest boiling point selected for retrieval component, which represents the high-molecular almasoud, in conditions which ensure the preservation selected to extract the component or components constituting the high-molecular alasoini, processed in the source reagent in the amount recoverable; and

C) heat treatment of the source reagent extracted in the operation (b) pyrolysis of at least a sufficient number of components contained in it, not I have which is almatadema, to retrieve the selected component or components constituting the high-molecular alasoini from heat-treated source reagent, and the pyrolysis is carried out in conditions which ensure the preservation of the processed source reagent selected component or components constituting the high-molecular alasoini, in the amount recoverable.

15. The method according to 14, in which the reagent additionally contains components that are not almatadema, having a boiling point both below and higher than the lowest boiling temperature of the selected component, representing macromolecular almasoud, and at least one component representing low-molecular almasoud.

16. The method according to 14, further comprising the operation (g) extracting a composition enriched in one or more selected components constituting the high-molecular alasoini, processed from the specified source reagent obtained in operation (b)through one or more additional separation methods selected from the group consisting of chromatographic methods, methods based on thermal diffusion, zone cleaning, successive recrystallization and means separation by size.

17. The method for extracting structure from the source at glevodorodnogo raw materials, enriched with one or more selected components constituting the high-molecular alasoini, including the following:

a) selecting a source reagent containing one or more selected components constituting the high-molecular alasoini, in the amount recoverable, and unselected substances, including components that are not almatadema;

b) separation of the source reagent into fractions with obtaining one or more selected fractions enriched with substances that have values of boiling point in the range of from a temperature lower than the boiling temperature of the selected component, representing macromolecular almasoud with the lowest boiling point to a temperature higher than the boiling temperature of the selected component, representing macromolecular almasoud with the highest boiling point;

C) thermal decomposition of one or more of these selected fractions of pyrolysis, at least, a sufficient number of contained components that are not almatadema, in terms of providing one or more thermally processed fractions, preserving the high-molecular almasoud in the amount recoverable; and

g) removing the composition containing the same is or more selected components, representing high alasoini, from one or more specified thermal processed selected fractions obtained in operation (b)through one or more additional separation methods selected from the group consisting of chromatographic methods, methods based on thermal diffusion, zone cleaning, successive recrystallization and means separation by size.

18. Means for retrieving at least one selected macromolecular almasoud from the source of hydrocarbons, including

the choice of the source reagent containing at least one selected macromolecular almasoud in the amount recoverable, in a mixture with substances that are not almatadema, aromatic and polar components

distillation of the source reagent with getting the top and bottom fractions, and the bottom fraction contains at least one selected macromolecular almasoud,

the separation into fractions of the lower fractions with getting the top fraction containing at least one selected macromolecular almasoud, mixed with substances that are not almatadema, aromatic and polar components

pyrolysis top fraction to reduce the concentration of substances that are not almatadema, and get the lead is bent pyrolysis top fraction,

processing subjected to pyrolysis top fraction by liquid chromatography low pressure to remove aromatic and polar components and obtain a top fraction is subjected to pyrolysis and the treated liquid chromatography low pressure, and

removing at least one selected macromolecular almasoud from the top of the fraction subjected to pyrolysis and the treated liquid chromatography low pressure, using the final chromatographic method.

19. The method according to p in which the final chromatographic method is gas chromatography.

20. The method according to p in which the final chromatographic method is liquid chromatography high pressure.

21. The method according to claim 20, in which liquid chromatography high pressure includes chromatography on two consecutive liquid chromatographic columns, two columns have different selectivity.



 

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1 tbl, 8 ex

FIELD: petrochemical industry; methods of production of styrene.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of production of styrene. The invention provides for dehydrogenation of the ethylbenzene charge gained after mixing of the fresh ethylbenzene with the recycled ethylbenzene on the ferrioxide catalytic agent at presence of the steam at the mass ratio of the raw to the steam of no less than 1:2, at the temperature of 580-640°С and the volumetric speed of feeding of the ethylbenzene charge of 0.23-0.45 m3/h. The hydrocarbon condensate (the product of the dehydrogenation) containing styrene, the unreacted ethylbenzene, the by-products including the phenyl acetylene impurity before the stage of the rectification is hydrogenated using the palladium-containing catalytic agents at the temperature of 20-30°С, the volumetric speed of 4.5-5.0 m3/h-1 and at the volumetric ratio of the hydrogen : raw - 35-45. The technical result of the invention is the increased purity of the produced styrene without reduction of productivity of the whole process of the marketable styrene.

EFFECT: the invention ensures the increased purity of the produced styrene without reduction of productivity of the whole process of the marketable styrene.

1 tbl, 8 ex

FIELD: petrochemical processes.

SUBSTANCE: process involves extractive rectification in presence of extractant mainly containing aliphatic N-alkylamide, while toluene is introduced into rectification column point disposed between extractant inlet and the top of column.

EFFECT: reduced loss of extractant with distillate.

6 cl, 3 dwg, 6 tbl, 6 ex

FIELD: petroleum chemistry, polymers, in particular styrene production.

SUBSTANCE: invention relates to method for production of phenol-based co-inhibitor of styrene thermopolymerization comprising acid condensation reaction of by-product-coking phenols containing mono- and dihydric phenols in mass ratio (1.3-2):1, with sulfuric acid at elevated temperature followed by catalytic oxidation of obtained phenol oligomer with hydrogen peroxide and neutralization of acid catalyst with sodium nitrite to produce modified product, wherein component ratio (mass pts) of extractive (total) by-product-coking phenols:sulfuric acid:hydrogen peroxide:sodium nitrite is 100:1.5-2.0:30-33.0:2.1-2.8. Also described is two-component composition for inhibiting of styrene thermopolymerization containing Mannich's base and co-inhibitor in mass ratio of 1:(1-2), wherein as co-inhibitor composition contains modified product of by-product-coking phenols.

EFFECT: effective inhibitor with good solubility in treated product; enhanced assortment of inhibitors.

3 cl, 2 tbl, 18 ex

FIELD: chemical industry; diamond-mining industry; methods of cleaning of the high-molecular diamond-likes.

SUBSTANCE: the invention is pertaining to the methods of extraction and cleaning of the high-molecular diamond-likes from the hydrocarbons raw materials. The invention provides, that at first they conduct selection of the initial reactant containing tetramantan and others high-molecular diamond-likes, removal from the reactant the components having the boiling temperature less, than the lowest temperature of boiling of tetramantan, and the thermal treatment of the rest for pyrolysis. The pyrolysis is conducted under the conditions providing preservation of tetramantan and other high-molecular diamond-likes. The composition is enriched with the tetramantan and other high-molecular diamond-likes and contains the tetramantan and pentamantan in amount of 10 mass % and 0.5 mass % accordingly with respect to the other the other diamond-likes. The invention allows to produce the compositions containing the high-molecular diamond-likes from the natural raw materials.

EFFECT: the invention ensures production of the high-molecular diamond-likes from the natural raw materials.

21 cl, 7 tbl, 15 ex, 40 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diisobutylaluminum chloride (i-Bu2AlCl) in the presence of zirconocene dichloride catalyst (Cp2ZrCl2) at molar ratio of C60:i-Bu2AlCl:Cp2ZrCl2=1:(55-65):(0.15-0.25), preferably 1:60:0.20, in argon atmosphere in the absence of light at room temperature of 60-100°C and atmospheric pressure in toluene medium for 1-5 hours, with further hydrolysis of reaction mass. The method allows obtaining total 77-91% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diethylaluminium chloride (Et2AlCl) in the presence of magnesium powder and titanocene dichloride catalyst (Cp2TiCl2) at molar ratio of C60:Et2AlCl:Mg:Cp2TiCl2=1:(110-130):(55-65):(0.15-0.25), preferably 1:120:60:0.20, in argon atmosphere in the absence of light at room temperature of (20-21°C) and atmospheric pressure in toluene and tetrahydrofuran medium for 1-3 hours, with further hydrolysis of reaction mass. The method allows obtaining total 70-88% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diisobutylaluminum hydride (i-Bu2AlH) in the presence of zirconium tetrachloride catalyst (ZrCl4) at molar ratio of C60:i-Bu2AlH:ZrCl4=1:(55-65):(0.15-0.25), preferably 1:60:0.20, in argon atmosphere in the absence of light at room temperature of (20-21°C) and atmospheric pressure in toluene medium for 1-5 hours, with further hydrolysis of reaction mass. The method allows obtaining 73-87% of polyhydro[60]fullerene output after reaction mass hydrolysis.

EFFECT: improved method.

7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with ethylaluminium dichloride (EtAlCl2) in the presence of magnesium powder and titanocene dichloride catalyst (Cp2TiCl2) at molar ratio of C60:EtAlCl2:Mg:Cp2TiCl2=1:(55-65):(55-65):(0.15-0.25), preferably 1:60:60:0.20, in argon atmosphere in the absence of light at room temperature of (20-21°C) and atmospheric pressure in toluene and tetrahydrofuran medium for 1-3 hours, with further hydrolysis of reaction mass. The method allows obtaining 72-86% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (I): , involving fullerene C60 interaction with aluminium trichloride (AlCl3) in the presence of magnesium powder and zirconocene dichloride catalyst (Cp2ZrCl2) at molar ratio of C60:AlCl3:Mg:Cp2ZrCl2=1:(95-105):(95-105):(0.15-0.25), preferably 1:100:100:0.20, in argon atmosphere in the absence of light at room temperature of (20-21°C) and atmospheric pressure in toluene medium for 2-4 hours, with further hydrolysis of reaction mass. The method allows obtaining total 80-94% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for combined synthesis of C60-Ih)[5,6]fullero[2',3':1,9]cyclopropane and 1'(2')a-homo(C60-Ih)[5,6]fullerene of general formulae and by reacting C60-fullerene with an ether solution of diazomethane (CH2N2) and subsequent conversion of the obtained fulleropyrazoline into a formula (1) and (2) compound, characterised by that both reactions take place simultaneously during reaction of C60-fullerene with diazomethane in toluene in the presence of a palladium catalyst (Pd(acac)2), taken in molar ratio C60: diazomethane: Pd(acac)2=0.01:(0.01-0.03):(0.0015-0.0025), preferably 0.01:0.02:0.002, at temperature 40°C for 0.5-1.5 hours.

EFFECT: obtaining end products with higher output.

1 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 1'(2')a-homo(C60-Ih)[5,6]fullerene of general formula (1): characterised by that C60-fullerene reacts with ether solution of diazomethane (CH2N2) in o-dichlorobenzene in the presence of a palladium catalyst (Pd(acac)2), taken in molar ratio C60 : diazomethane : Pd(acac)2= 0.01:(0.01-0.03):(0.0015-0.0025), at room temperature (approximately 20°C) for 0.5-1.5 hours.

EFFECT: use of the present invention enables to achieve higher output of end products using a palladium complex in catalytic quantities, as well as low power consumption.

1 cl, 7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing (C60-Ih)[5, 6]fullero[2',3':1,9]cyclopropane of general formula (1): , characterised by that C60-fullerene reacts with diazomethane (CH2N2), generated in situ from N-methyl-N-nitrosourea and aqueous solution of KOH in chlorobenzene in the presence of a palladium catalyst (Pd(acac)2), taken in molar ratio C60: N- methyl-N-nitrosourea: Pd(acac)2=0.01:(0.01-0.05):(0.0015-0.0025) and 0.1 ml of 40% aqueous solution of KOH, preferably 0.01:0.03:0.002, at temperature 40°C for 0.5-1.5 hours.

EFFECT: use of the present method enables to use a palladium complex in catalytic amounts and obtain an end product with higher output.

1 cl, 7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing cycloalkylidenehomo(C60-Ih)[5,6]fullerenes of general formula (1): n=1,2,3,4, characterised by that C60-fullerene reacts with cyclic diazo-compounds, generated in situ from corresponding unsubstituted hydrazones () using Ag2O, in o-dichlorobenzene in the presence of a three-component catalyst system Pd(acac)2-2PPh3-4Et3Al, taken in molar ratio C60 : unsubstituted hydrazone : Pd(acac)2-2PPh3-4Et3Al = 0.01 :(0.01 -0.02):(0.0015-0.0025), at room temperature (approximately 20°C) for 20-40 minutes.

EFFECT: method differs from existing methods by high output of end products and selectivity of the reaction, use of a palladium complex in catalytic amounts, as well as low power consumption.

1 cl, 10 ex, 1 tbl

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