JP6813834B6 - Methods and Programs to Approximately Identify the Molecular Structure of Multicomponent Mixtures (CSA2) - Google Patents

Description

The present invention relates to a method of identifying the molecular structure of each component constituting a multi-component mixture using a computer. Furthermore, it relates to a method of determining a composition model of a multi-component mixture. It also relates to a program for executing those methods.

In the operation of various equipment related to petroleum refining, raw material oils are usually analyzed based on overall physical properties such as specific gravity, viscosity, and distillation properties (boiling point), and in oil types with similar past data. A method is adopted in which the operating conditions are determined with reference to the operating results.
However, with this method, it is not easy to search for similar past data in an era where imported crude oil types are diversifying as it is now, and from the viewpoint of improving operating efficiency, past operation is simply performed. It is no longer just a matter of following the achievements.
Therefore, instead of grasping from a collective viewpoint such as specific gravity, viscosity, and distillation properties, we grasped the chemical structure and abundance ratio at the level of hydrocarbon molecules that make up petroleum, and estimated it. It has been considered that if the operating conditions can be set based on the knowledge of the physical property values and the like, efficient operation based on more objectivity can be performed. Therefore, in the petroleum industry, the emergence of technology for grasping petroleum at the molecular level has been awaited.
However, petroleum is a mixture of a huge number of hydrocarbon molecules, and especially in heavy oil, the chemical structure of each of these molecules is specified, and the abundance ratio of each of them is also specified. Was very difficult.

Until now, when analyzing petroleum at the molecular level and analyzing its chemical structure, a technique for measuring the molecular weight with high accuracy using a mass spectrometer based on the Fourier transform ion cyclotron resonance method, which is a high-resolution mass spectrometer, has been used. It was. For example, it is the method described in Patent Document 1 or Patent Document 2.
In particular, in Patent Document 2, by colliding the molecules constituting petroleum with argon or the like, the crosslinked portions of the molecules are cut and decomposed into core portions composed of them, and their chemical structures are obtained. A method for estimating the molecular structure is described later, in which they are combined to reconstruct the original molecule.

Special Table 2014-500506 Japanese Patent Publication No. 2014-503816

However, in the method described in Patent Document 2, it is determined based on the probability which part and which part are selected and combined to construct the molecule for the parts forming the molecule such as core, crosslink, and side chain. That is. Therefore, even if the molecular structure of the components was constructed in the same process based on a certain mass spectrometric data, the obtained results would be different for each construction work. This was unavoidable as long as the concept of "probability" was used to construct the molecular structure. That is, the method described in Patent Document 2 has a fatal defect that the constantness and reproducibility of the obtained results are not guaranteed and "the operational stability of the apparatus cannot be ensured".
In the prior art, it was not possible to devise a systematic theory and ingenuity for constructing a molecular structure, so we had to accept and use the idea of probability theory, which is inherently uncertain. It was. That is, it is effective for the purpose of specifying the structure and abundance ratio of individual molecules in the special object of petroleum, which is a mixture of a huge number of hydrocarbon molecules of hundreds of thousands or more. The reality was that the theory could not be constructed and there was no other way than to bring in "probability theory".

The present invention has been made under such circumstances, and an object of the present invention is to provide a method for identifying the molecular structure of each component constituting a multi-component mixture with a certain degree of certainty using a computer. It is also an object of the present invention to provide a method for determining a composition model of a multi-component mixture, and to provide a program for carrying out these methods.
Furthermore, to provide a method for estimating the physical property value of the multi-component mixture based on the molecular structure of each component constituting the multi-component mixture and its abundance ratio specified by the above method, estimated by such a method. It is an object of the present invention to provide a method of operating an apparatus relating to a multi-component mixture, particularly petroleum, characterized in that operating conditions are set based on the physical property values of the multi-component mixture.

In order to achieve the above object, the present inventors have created the following inventions. That is, one of the present inventions is a method of specifying the molecular structure of each component constituting the multi-component mixture and the abundance ratio thereof using a computer.
In step 1, mass spectrometry is performed on the multi-component mixture, the molecular formula of the molecule belonging to the peak is specified for each of the obtained peaks, and the abundance ratio of the molecule is further specified.
Both the optimum structure X when the molecule belonging to each of the peaks obtained in the mass spectrometry in step 1 is single core and the optimum structure Y when it is multi-core are specified. Step 2 and
Step 3 for determining whether the molecule belonging to each of the peaks obtained by the mass spectrometry in step 1 is single-core or multi-core, and
In response to the determination in step 3, either the structure X or the structure Y specified in step 2 is adopted, and the side chain and the crosslink are determined and assigned to the adopted core portion in step 4. It is characterized by including.

Further, another present invention is a method for specifying the molecular structure of each component constituting the multi-component mixture and the abundance ratio thereof with respect to the multi-component mixture using a computer.
In step 1, mass spectrometry is performed on the multi-component mixture, the molecular formula of the molecule belonging to the peak is specified for each of the obtained peaks, and the abundance ratio of the molecule is further specified.
Both the optimum structure X when the molecule belonging to each of the peaks obtained in the mass spectrometry in step 1 is single core and the optimum structure Y when it is multi-core are specified. Step 2 and
In the peak obtained by the mass spectrometry in step 1, the peaks that can take both single core and multi-core are assumed to take both single core and multi-core, respectively, and the abundance ratio of single core and multi-core in the peak is determined. Step 3 and
In response to the determination in step 3, the structure X specified in step 2 is adopted for the single core, and the structure Y specified in step 2 is adopted for the multi-core, and the adopted core portion is used. On the other hand, it is characterized by including step 4 of determining and allocating side chains and crosslinks.

In addition, another invention is a method for determining a composition model of a multi-component mixture, and is a program for executing these methods.
Further, another invention is a method for estimating the physical property value of the multi-component mixture based on the molecular structure of each component constituting the multi-component mixture and the abundance ratio thereof, which is specified by the above method. It is a method of operating an apparatus relating to a multi-component mixture, preferably petroleum, characterized in that operating conditions are set based on an estimated physical property value of the multi-component mixture.

In identifying the molecular structure of each component of a multi-component mixture, the present invention provides a novel and groundbreaking theory based on deep insights based on broad insight into mass spectrometry and various outstanding points of view. It was made based on what was constructed.
In each step included in the method of the present invention, various unique rules and assumptions are skillfully set. However, these rules and assumptions are not set without technical grounds, but as a result of thorough examination of "what points should be held to ensure the necessary and sufficient effectiveness in reality". It was devised.
Furthermore, we discuss how detailed and accurate the chemical structures of each of the vast numbers of molecules that make up petroleum need to be ensured. As a result of careful examination, we came up with an epoch-making display method called "JACD", which will be described later. This "JACD" is a new method for displaying the structural information of molecules, but by creating this method, it is possible to obtain structural information at a necessary and sufficient level even for macromolecules such as asphaltene. It became.

In this way, the method of the present invention is not a method that includes the uncertainty of the conventional "probability theory", but is based on skillfully fusing the theory and various creations devised by the inventors, so to speak. It is a "deterministic" method.

Since the present invention is a method of identifying a molecular structure by a "deterministic" approach, the same result is surely obtained every time. The use of the word "determinism" is based on this fact. This ensures that the same results are always obtained in the analysis of raw materials when operating an oil refinery, and the contribution to ensuring stability is immeasurable.
Further, in the present invention, the molecular structure of each component constituting the multi-component mixture, that is, various atomic groups existing in the molecule is specified. Therefore, if a known atomic group contribution method is used, the molecule is specified. It is possible to estimate various physical property values of the atom with extremely high accuracy. Further, since the abundance ratio of each component is also specified, if this abundance ratio is taken into consideration, it is possible to estimate the physical characteristic value of the entire multi-component mixture from the physical characteristic value of each component.
In petroleum refining equipment, the optimum conditions are usually set and operated using the various physical property values of the raw material oil as a direct guideline or an indirect guideline, but the high accuracy obtained by the method of the present invention is high. It becomes possible to use various physical property values, which further contributes to the improvement of efficiency.
As described above, the present invention is an epoch-making one that solves the difficult problems inherent in the prior art at once, and exerts an exceptional effect in terms of application to the actual oil industry. It is a thing.

It is a flowchart explaining the method by embodiment of this invention. It is a flowchart explaining the method by another embodiment of this invention. It is a JACD display example of a mass spectrum obtained by FT-ICR-mass spectrometry and a molecule belonging to a certain peak. It is a chart of the mass spectrum measured by FT-ICR-mass spectrometry. It is a figure explaining the distinction between a single core and a double core in a mass spectrum chart. It is a chart of the mass spectrum obtained by FT-ICR-mass spectrometry for a polycyclic aromatic resin (PA). For the polycyclic aromatic resin (PA), in the chart of the mass spectrum obtained by FT-ICR-mass spectrometry, the peak is divided into a single core and a double core.

Hereinafter, embodiments of the present invention will be described.
First, terms and expressions used in the present specification will be described.
(1) "Multi-component mixture"
A "multi-component mixture" is a concept that includes any mixture consisting of two or more components. The content ratio of the ingredients does not matter. Specifically, it preferably means "petroleum", and more preferably means "heavy oil".
In the present invention, more specifically, it means "a mixture containing many aromatic compounds as main components".

(2) "Ingredients", "Constituent"
The "component" in "each component constituting the multi-component mixture" is regarded as "an aggregate of molecules recognized to belong to the same molecular species", which is each member constituting the multi-component mixture. Is preferable. Here, "identical" may be regarded as meaning "the molecular structure is completely specified and then the same", or "isomers in the molecular structure (molecular formulas are the same)". Although they have different structures), they may be regarded as the same meaning, or may be regarded as, for example, meaning that they are the same in the structure specified by a method such as JACD, which will be described later. .. Furthermore, it may be broadly regarded as "an aggregate of molecules grouped together based on an arbitrarily determined standard".
Further, "constituting" does not have to assume 100% of all the components present in the multi-component mixture. Depending on how the molecular structure of each component specified by the present invention is used, "each constituent component" is appropriately determined according to the degree of detail required to specify the molecular species as a component. do it. For example, only molecular species having a certain abundance (absence ratio) or more in a multi-component mixture may be regarded as "constituent components". It is not always necessary to identify the molecular structure of all of a huge variety of molecular species such as petroleum, and molecular species that exist only in trace amounts may be ignored if necessary. For example, in the present specification, where a polycyclic aromatic resin (PA) is described as a "multi-component mixture", a paraffin-based component of the polycyclic aromatic resin (PA) is used. In some cases, the presence of compounds and olefin compounds is ignored.

(3) "Specify the molecular structure", "Molecule"
"Specifying a molecular structure" includes any act of specifying some information about the structure of a molecule with respect to the "molecule" in the above "component". The degree of theoretical accuracy and the display method of the specified structure are not particularly limited. The degree and display method may be appropriately selected according to the purpose and necessity. This includes not only the act of specifying the structure of the entire molecule, but also the act of incorporating and specifying information on the structure of a part of the molecule. For example, a specific method of specifying only the structure of the core portion and leaving the structure of the side chain portion and the crosslinked portion as the molecular formula is also applicable.
As a specific method, a display method called JACD, which will be described later, is preferably used. In the present specification, when "the molecular structure is specified", it means that it is specified by JACD. The molecule whose structure is specified by "JACD" is a concept including all isomers due to the difference in the binding position of the attributes described later.
In the present specification, the word "molecule" may be regarded as a concept including all isomers.

(4) "Specify the abundance ratio of each component"
The accuracy of "specifying the abundance ratio of each component" does not matter as long as it is an act of specifying the abundance ratio of each component constituting the mixture. Nor does it mean that the abundance ratio must be specified for all component species that make up the mixture. That is, only when the abundance ratios of all the components including the components that are difficult to detect by the analytical technique and the components that do not need to be specified are specified, "the abundance ratio of each component is specified. It is not something that says. Such trace components and the like may be collectively treated as "other components". Furthermore, these need not be excluded from the range of "each component constituting the mixture" and not included in the denominator for calculating the abundance ratio of other components.

(5) "All"
If the word "all" in the present specification is taken to literally mean "perfectly 100% all", the present invention may not be effective as a technique. In addition, the accuracy of the description in this specification may not be guaranteed.
Therefore, for example, the phrase "all peaks" in the mass spectrum literally means not only "perfectly 100% all peaks" but also, for example, for the purpose of consideration in that situation. Peaks related to molecules that are not always necessary and peaks that are difficult to distinguish may be considered to mean peaks other than those peaks after being appropriately excluded. The same applies to the part where the term "all cores" is used, and not only the meaning of "perfectly 100% all cores" but also selection or exclusion as appropriate according to the required accuracy and purpose. It means that you can do it.

(6) "Peak"
The horizontal axis of the peak obtained in mass spectrometry is m / z for the molecular ion or pseudomolecular ion of each component constituting the multi-component mixture. Since the numerical value indicated by this m / z is a numerical value corresponding to the mass of a molecular ion or a pseudo-molecular ion, it generally represents the molecular weight of the molecule attributed to the peak.
The exact notation of m / z is made in italics, but due to restrictions on the character type used as the patent application document, in the present specification, it is expressed in the usual typeface for convenience.
In the present specification, this "peak of m / z for molecular ions or pseudomolecular ions obtained in mass spectrometry" may be referred to as "peak obtained in mass spectrometry" or simply "peak".
The height of the peak indicates the relative abundance ratio of the molecules belonging to the peak.

(7) "Molecular formula"
The "molecular formula" is a formula showing only the types and numbers of the elements constituting the molecule, and the structure is not specified. Since the types and numbers of the elements constituting the molecule are known, information such as the molecular weight and the DBE value described later can be obtained.
In mass spectrometry by the Fourier transform ion cyclotron resonance method (hereinafter, sometimes referred to as "FT-ICR-mass spectrometry") mainly used in the present invention, the value of m / z is determined up to the fourth digit. Can be done. Therefore, the molecular formula of the molecule belonging to the peak can be determined by precisely adjusting the mass numbers in consideration of the presence of the isotope of the atom. Since the molecular formula only represents the type and number of elements constituting the molecule, it means that a plurality of isomers may exist as the molecule corresponding to the above-determined molecular formula. That is, a plurality of isomers having the same molecular formula belong to one peak.
However, due to the characteristics of FT-ICR-mass spectrometry, even if the molecular formula is the same, the mass will be different from the original molecular ion, for example, due to the addition of hydrogen ions to the molecular ion, so it is different. May appear as a peak of. Therefore, even if the peaks appear as different peaks in the measurement, those having the same type and number of elements constituting the molecular formula may be regarded as "the same one molecular formula". In the phrase "molecule corresponding to the molecular formula", "the molecular formula" may be understood to mean such "the same one molecular formula". Further, the term "certain peak" may be considered as a concept that collectively captures all the peaks of various m / z that are said to represent "the same one molecular formula" in the above sense.

(8) "Core", "Single core", "Double core", "Core part"
The "core" is a kind of "attribute" described in the section of "JACD" described later, and specifically, the aromatic ring or the naphthenic ring itself, and the aromatic ring and the naphthenic ring are not crosslinked. Those that are directly bonded, those in which a heterocycle is directly bonded to an aromatic ring or a naphthenic ring rather than a crosslink. Since cross-linking or side chains are attributes separate from the core, the term "core" means having no cross-linking or side chains.
On the other hand, "single core" is a concept that refers to a molecule having only one core. Since it is a concept that refers to a molecule, it also includes those with side chains attached to the core. A molecule in which two or more of the cores are crosslinked is called a "multi-core". Since "multi-core" also means a molecule, it also includes those having a side chain bonded to the core. By the way, a molecule formed by cross-linking two cores is called a "double core".
For example, the following naphthalene molecule is a "single core" because it is composed of one aromatic ring, and is not a double core composed of two benzene rings.

The "core portion" is used to particularly refer to the "core" portion of the single-core molecule or double-core molecule described above.

(9) "DBE value"
The "DBE value" is a value calculated by the following formula (1) when the molecular formula is "CcHhNnOoSs".
DBE = c−h / 2 + n / 2 + 1 ・ ・ ・ (1)
(However, c is the number of carbon atoms, h is the number of hydrogen atoms, n is the number of nitrogen atoms, o is the number of oxygen atoms, and s is the number of sulfur atoms.)
This value generally indicates the degree of unsaturatedness in the molecule, especially the presence of double bonds and rings.

(10) "JACD""Juxtaposed Attributes for Chemical-structure Description"
"JACD" is a new display method for molecular structure, and displays the molecular structure according to the type of attribute and the number of attributes. It does not show where the attributes are combined in other attributes.
In the above, the "attribute" is a concept that refers to a chemical structural part that constitutes a molecule. In the case of aromatic compounds, it specifically refers to the above-mentioned "core", "crosslink" and "side chain".
In this display method, the present inventors carefully examined how detailed the structure of each of the enormous number of molecules constituting petroleum should be specified. As a result of this, it was devised.
In the first place, when displaying a molecule, there are methods called molecular formula, demonstrative formula, and structural formula, and the amount of information about the chemical structure increases in this order, but in the case of petroleum, which is a mixture of various molecules including macromolecules. , It is almost impossible to accurately identify the structural formula of each molecule existing in the molecule.
Therefore, the present inventors have devised a new method for displaying a molecular structure called "JACD".
The molecule represented by the following chemical formula will be described as an example.

This compound is represented by JACD as shown in Table 1 below.

A molecule whose structure is specified by "JACD" is a concept that includes all isomers due to differences in the binding positions of attributes.

(11) "Physical characteristics"
The "physical property value" is specifically exemplified below, but is not limited to these, and is a value obtained based on the molecular structure specified by the above method and its abundance ratio. Therefore, if it expresses the physical or chemical properties, properties, and properties of a substance, it shall be included in the "physical property value" regardless of the name.
Gibbs produced Free energy, ionization potential, polarization rate, dielectric constant, vapor pressure, liquid density, API degree, gas viscosity, liquid viscosity, surface tension, boiling point, critical temperature, critical pressure, critical volume, heat generated, heat capacity, bipolar Moment, enthalpy, entropy, etc.

(12) "Petroleum", "Petroleum-related equipment"
In the present specification, the term "petroleum" is used not only for crude oil, but also for fractions obtained by distilling crude oil and fractions obtained by subjecting fractions to treatment by a secondary device such as reforming or decomposition. Will be used as a generic concept including. Alternatively, a fraction obtained by distilling crude oil may be further fractionated into components such as saturated hydrocarbons and aromatic hydrocarbons.
"Petroleum-related equipment" includes all equipment related to petroleum processing, such as distillation equipment and extraction equipment, reforming equipment, hydrogenation reaction equipment, desulfurization equipment, and other equipment that involves a chemical reaction. "Petroleum-related equipment" is sometimes collectively referred to as "petroleum refining equipment."

Next, each step in the present embodiment will be described with reference to the flowchart of FIG.
(1) Step 1 (mass spectrometry) (S1 in FIG. 1)
The first step is to perform mass spectrometry on the multi-component mixture, specify the molecular formula of the molecule belonging to the peak for each of the obtained peaks, and further specify the abundance ratio of the molecule. In other words, mass spectrometry, preferably FT-ICR-mass spectrometry, is performed on the multi-component mixture to identify the molecular formulas of the molecules belonging to each peak for all the peaks obtained, and further correspond to the molecular formulas. It is a step to specify the abundance ratio of the molecule to be used. That is, it is a step of specifying the molecular formula of each component constituting the multi-component mixture and the abundance ratio of the molecule corresponding to the molecular formula.

For mass spectrometry, it is preferable to use an ultra-high resolution mass spectrometer. Specifically, it may be referred to as a mass spectrometer based on the Fourier transform ion cyclotron resonance method (hereinafter referred to as "FT-ICR-mass spectrometer". Further, the mass spectrum obtained by FT-ICR-mass spectrometry is referred to as "FT-". It may be referred to as "ICR-mass spectrum". In general, the wording "FT-ICR-mass spectrometry" may be used as appropriate. Further, these words are also used in the above and in the brief description of the drawings. ) Is used to soft-ionize a known method, that is, a multi-component mixture to form a molecular ion or a pseudo-molecular ion, thereby performing highly accurate measurement.
FT-ICR-mass spectrometry can determine the value of m / z to the fourth decimal place. Therefore, the molecular formula of the molecule belonging to the peak can be determined by precisely adjusting the mass numbers in consideration of the presence of the isotope of the atom. A plurality of molecules having the same molecular formula belong to one peak.
By the way, depending on the type and number of heteroatoms and the DBE value in the obtained molecular formula, there are cases where the molecule belonging to the peak can have only a single core or only a multi-core due to its structure. There is.
The ratio of the height of a peak to the sum of the heights of all peaks represents the abundance of molecules belonging to that peak.

(2) Step 2 (Specification of the structure of the core part of the molecule) (S2 in FIG. 1)
In step 2, both the optimum structure X when the molecule belonging to each of the peaks obtained by the mass spectrometry in step 1 is single core and the optimum structure Y when it is multi-core. Is the step to identify.

Step 2 is preferably performed as follows.
(A) First, all the cores that can be taken by the molecule belonging to each peak are listed by the following procedures i to iv.
i. In step 1, for each peak obtained from the FT-ICR-mass spectrometry, information on the molecular formula of the molecule attributed to the peak, the type and number of heteroatoms contained in the molecular formula, and the DBE value is obtained. I was able to do it.
ii. Based on the type and number of heteroatoms and the DBE value, all corresponding cores are listed.
In this enumeration, a list of various cores that can be assumed to exist in each molecule constituting petroleum (that is, a "core structure list" described later) is prepared in advance, and obtained in the above i. It is preferable to collate the type and number of heteroatoms and the DBE value, and select all the cores and core combinations that are considered to be applicable from the list.

iii. Core structure list The types of cores to be stored in the above core structure list are not particularly limited and may be anything, but the validity of selecting the cores to be stored is the validity of specifying the structure of each core. Will be directly connected to.
It is preferable to prepare a "core structure list" in advance according to the content of the multi-component mixture itself as a sample. For example, when the multi-component mixture is petroleum, a "core structure list for identifying the molecular structure of petroleum" can be prepared in advance based on many knowledge about petroleum so far, and it can be used. Good.
In creating the list, the number of rings in the basic aromatic ring, the type and number of naphthenic rings directly bonded to the aromatic ring (including the difference between cata-type and peri-type), and the mode of direct bonding (that is, the basic aromatic ring). It is advisable to store an appropriate number of cores in consideration of various conditions such as (aspect of how and where the naphthenic ring is bonded).
For example, the size of the aromatic ring is limited to 6 rings, the heteroatoms are assumed to be N, O, and S, and the number of heterocyclic rings is about 10. For convenience of calculation, a list is created. do it.

iv. Selection from the core structure list As the cores that can be taken by the molecules belonging to each peak, the corresponding cores are selected from the core structure list and listed. For that purpose, first, the types of heteroatoms are selected from the core structure list. Select a core that matches the number and DBE value.
In this selection, it is necessary to select all cores or combinations of cores, not only when the molecule is single core but also when it is multi-core. That is, in the case of a single core, selection may be made based on the type and number of heteroatoms possessed by the core and the DBE value itself, but in the case of a multi-core, for example, in the case of a double core, the two The sum of the types and numbers of the heteroatoms of the cores and the sum of the DBE values will be selected as a "combination of two cores" so as to match the type and number of the heteroatoms and the DBE value as a reference. The same procedure may be performed when there are three cores. Theoretically, there may be four or more, but if there are four or more, the calculation on the computer may become complicated, so a rule may be set that does not consider the case of four or more. The case of two is preferable.

In the above, the "type and number of heteroatoms" specifically means "the number of heteroatoms for each type of heteroatom". In this specification, the term "type and number of heteroatoms" is used in this sense. Since the hetero atom is preferably a nitrogen atom, a sulfur atom and an oxygen atom, the "type and number of hetero atoms" is preferably "the number of each of the nitrogen atom, the sulfur atom and the oxygen atom". You can also. Therefore, when it comes to heteroatoms, two so that "the number of nitrogen atoms, the number of sulfur atoms, and the number of oxygen atoms all match" matches the standard "type and number of heteroatoms". The above cores will be selected as a "combination".
Hereinafter, a case where two cores are crosslinked will be described as an example.

(B) Next, from the cores listed above, the molecules belonging to the peaks are the best candidates for the core portions in both the case where the molecule is single core and the case where the molecule is double core. , Each one is specified. The method for specifying is not limited, but is preferably performed as in i and ii below, for example.
i. In the case of a single core, among the several applicable cores listed above, the one having the smallest number of hydrogens bonded to the aromatic ring in the core is specified as the optimum structure X.

ii. If it is a double core, it is bonded to the aromatic ring in one of the "combination of two cores" listed above, which forms the "combination of two cores". Priority is given to the "combination" that has the smallest number of hydrogens. Next, for the selected "combination", the one having the smallest difference in the number of hydrogens bonded to each aromatic ring in the two cores forming the same is specified as the optimum structure Y.
As described above, as the molecules belonging to all the peaks in step 2, the optimum structure X when the molecules belonging to each of the peaks obtained in the mass spectrometry in step 1 are single cores and multi-core. Both of the optimum structures Y, if any, have been identified.

(C) By the way, depending on the type and number of heteroatoms in the molecular formula obtained in step 1 and the DBE value, the molecule belonging to the peak can theoretically have only a single-core structure or only a multi-core structure. There may be cases where it is not possible. In theory, both single-core and multi-core structures can be adopted, but under the condition that the cores are selected from the cores stored in the core structure list, the type and number of heteroatoms and the DBE value are satisfied. In some cases, it may not be possible to have candidates for both single-core and multi-core structures.
In the present specification, when "only a single core structure can be taken or only a multi-core structure can be taken", both the above-mentioned meaning that it cannot be taken theoretically and the meaning that it cannot be taken due to the limitation of the core structure list. Shall point to.
In this way, when only a single core can be obtained, the optimum structure X may be specified by the same method as described above. In the case where only multi-core is possible, the optimum structure Y may be specified in the same manner.

(3) Step 3 (determination of single core or multi-core) (S3 in FIG. 1)
Step 3 is a step of determining whether the molecule belonging to each of the peaks obtained by the mass spectrometry in step 1 is single-core or multi-core.
Hereinafter, the case where the multi-core is a double core will be described as an example.
In this step, first, for each of the peaks obtained by FT-ICR-mass spectrometry, it is assumed that the molecule assigned to each peak corresponds to either single core or double core, and then single. It means to decide whether it is a core or a double core.
Determined by the following steps i to iii.

i. For all the peaks obtained by FT-ICR-mass spectrometry, the ratio of the sum of the peak intensities of the peak groups to which the single core is applicable and the sum of the peak intensities of each of the peak groups to be applicable to the double core is calculated. Ask. The procedure is as follows (a), (b), and (c).
I. First, by performing proton NMR analysis on the multi-component mixture, the state of hydrogen atoms (positions of hydrogen atoms in the chemical structural formula) existing in the multi-component mixture can be known. Further, by performing elemental analysis, it is possible to know the abundance ratios of carbon, hydrogen and heteroatoms constituting the multi-component mixture. By such macro analysis, the "unit structure" of the multi-component mixture can be virtually estimated. The molecular weight of the "unit structure" estimated in this way can also be estimated. However, since only information on the existence states of carbon, hydrogen, and heteroatoms can be obtained by this macro analysis, "monomers of unit structure" and "unit structures are bonded to each other via cross-linking". That is, it is indistinguishable from "a multimer of unit structure".

By the way, the average molecular weight of a multi-component mixture can be determined by a known method.
Comparing the "molecular weight of the unit structure" and the "average molecular weight", is the multi-component mixture a "monomer of the unit structure" consisting of one "unit structure" or "a large amount of the unit structure"? You will get information about whether the "body" also exists. When the "multimer of the unit structure" is also present, it is possible to obtain information on the proportion of the "monomer" and the "multimer".
Here, the following equation (1) is set.
P value (degree of polymerization) = "average molecular weight" / "molecular weight of unit structure" ... (1)
The P value (degree of polymerization) indicates the unit structure, that is, the proportion of the monomers present in the whole. That is, if the P value (degree of polymerization) is "1", it means that all that exist is a "unit structure", and if it is "2", all that exists is "consisting of two unit structures". It means that it is a thing (we will call it a "dimer"). Theoretically, if it exceeds "2", that is, there may be more than a trimer, but in consideration of the complexity of the calculation, it is assumed that there is no more than a trimer. Good. That is, the existence of a trimer or more is not considered, and it is assumed that it is composed of only a monomer and a dimer, and if it exceeds "2", it is treated as "2".
In addition, the value of "P value-1" indicates the abundance ratio of the dimer to the entire multi-component mixture.

B. On the other hand, in step 2, the optimum structure X when the molecule belonging to each of the peaks obtained in the mass spectrometry in step 1 is single core, and the optimum structure X when it is multi-core. Both of the structures Y have been identified, but here the following assumptions are made.
That is, it is assumed that among all the peaks, all the peaks whose m / z value is smaller than the N value correspond to the single core, and all the peaks larger than the N value correspond to the double core, with a certain m / z = N value as the boundary. To do. At this time, assuming that the sum of the peak intensities corresponding to the single core is MS and the sum of the peak intensities of all the peaks is MA, the value of "1- (MS / MA)" is "other than the single core". That is, the abundance ratio of "double core" is shown.

C. From the above ideas of a and b, it is assumed that the equation of the following equation (2) holds.
("Average molecular weight" / "Molecular weight of unit structure") -1 = 1- (MS / MA) ... (2)
Here, "(" average molecular weight "/" molecular weight of unit structure ") -1" on the left side is the above-mentioned a. Therefore, it shows the abundance ratio of the dimer. On the other hand, the right side "1- (MS / MA)" indicates the abundance ratio of the double core.
If the above equation holds, the value of "(" average molecular weight "/" molecular weight of unit structure ") -1" on the left side indicates the abundance ratio of the double core to the whole.
In this way, since the abundance ratio of the double core to the whole can be known, the abundance ratio of the single core and the double core can also be known.

ii. Next, at the abundance ratio of the single core and the double core obtained above, all the peaks obtained by the original FT-ICR-mass spectrometry are delineated and classified. That is, in all the peaks obtained by the original FT-ICR-mass spectrometry, the peaks are arranged in order from the one with the smallest m / z value, and the peak intensities are added up from the one with the smallest m / z value. Then, a line is drawn where the ratio of the total value to the total intensity of all peaks becomes the above-mentioned "presence ratio of single core and double core".
Of the categories divided by this line, the category with a small m / z value corresponds to the single core, and the category with a large m / z value corresponds to the double core. However, even in the peak group to which the double core is applicable, there are peaks that can only have a single core structure due to the structure such as the DBE value and the number of heteroatoms. These are treated as a single core. That is, conversely, there are peaks that can only have a double-core structure even in the peak group to which a single core is applicable. These are treated as double cores.
iii. From the above, it is determined whether each peak by FT-ICR-mass spectrometry corresponds to a single core or a double core.

(4) Supplement to step 3 (adjustment of single-core and multi-core decisions)
It may be preferable to coordinate and re-determine the single-core or multi-core determination made in step 3. (Hereinafter, the case where the multi-core is a double core will be described as an example.)
(A) If the molecules belonging to all the peaks obtained in step 1 are molecules capable of having both single-core and double-core structures, no adjustment is necessary.
(B) When some of the molecules attributed to the peak can have only a single core or only a double core, it is preferable to adjust the determination of single core or multi-core.

The adjustment procedure and method are as follows.
i. Each of the peaks obtained in the preparation step 1 is divided into three types, a peak that can take only a single core, a peak that can take only a double core, and a peak that can take both a single core and a double core, and the abundance ratio of each is calculated. .. Of the peaks obtained in step 1, the abundance ratio of peaks that can only take single cores is "S (%)", the abundance ratio of peaks that can only take double cores is "D (%)", and single cores and double cores. The abundance ratio of peaks that can take both is defined as "S & D (%)".
Further, the abundance ratio of the single core obtained in step 3 is defined as "RS (%)", and the abundance ratio of the double core is defined as "RD (%)".

ii. When the value of "S" is larger than the value of "RS" All the other peaks except the peak that can take only a single core among all the peaks are determined as applicable to the double core. On the contrary, when the value of "D" is larger than the value of "RD", all the peaks except the peak that can take only a double core are determined as applicable to a single core. ..
It is impossible that the value of "S" is larger than the value of "RS" and the value of "D" is also larger than the value of "RD".
As an example,
・ Existence ratio of peaks that can only be taken with a single core "S = 18 (%)",
・ Existence ratio of peaks that can only be taken by double core "D = 15 (%)",
・ Existence ratio of peaks that can take both single core and double core "S & D% = 67 (%)"
-The calculated single core abundance ratio obtained in step 3 is "RS% = 90 (%)",
Calculated double core abundance ratio is "RD = 10 (%)"
And.
In this case, all the peaks other than the peak that can take only a double core among all the peaks are determined as applicable to the single core.
The operation of dividing the original mass spectrum chart at 90/10 becomes unnecessary.
As a result, the peak ratio corresponding to the single core is 85%, and the peak ratio corresponding to the double core is 15%.

iii. When the value of "S" is smaller than the value of "RS" As an example
・ Existence ratio of peaks that can only be taken with a single core "S = 18 (%)",
・ Existence ratio of peaks that can only be taken by double core "D = 15 (%)",
・ Existence ratio of peaks that can take both single core and double core "S & D = 67 (%)"
-Calculated single core abundance ratio "RS = 25 (%)" obtained in step 3,
-Calculated double core abundance ratio "RD = 75 (%)"
And.
In this case, the peak with a single core is still RS-S = 25-18 = 7%.
Therefore, some of the peaks that can take both are allocated to the single core so that the ratio of the peaks that take a single core is 25% as a whole.
Of the peaks could be both, how much distributes minute single-core method, the peak can take both, from the lower of the value of m / z, the existing ratio of the peak single-core corresponds as a whole It is divided at 25%, and the category with the smaller m / z value corresponds to the single core, and the category with the larger m / z value corresponds to the double core.
As a result, the peak ratio corresponding to the single core is 25%, and the peak ratio corresponding to the double core is 75%.

iv. When the value of "D" is smaller than the value of "RD" As an example
・ Existence ratio of peaks that can only be taken with a single core "S = 18 (%)",
・ Existence ratio of peaks that can only be taken by double core "D = 15 (%)",
・ Existence ratio of peaks that can take both single core and double core "S & D = 67 (%)"
-The calculated single core abundance ratio obtained in step 3 is "RS = 80 (%)",
Calculated double core abundance ratio is "RD = 20 (%)"
And.
In this case, the peak having a double core is still RD-D = 20-15 = 5%.
Therefore, determine some of the peaks that can take both as double so that the ratio of peaks that take double cores is 20% as a whole. , From the one with the higher m / z value, divide the peak where the abundance ratio of the peak corresponding to the double core is 5% as a whole. It is assumed that the single core corresponds to the category having the smaller value of z.
As a result, the peak ratio corresponding to the single core is 80%, and the peak ratio corresponding to the double core is 20%.

(5) Step 3 of FIG. 2 as an alternative method (determination of the abundance ratio of single core and multi-core)
In step 3 of FIG. 2, in the peak obtained by the mass spectrometry of step 1, the peaks that can take both single core and double core are assumed to take both single core and double core, respectively. This is a step to determine the abundance ratio of double cores.
The step 3 is a step of assuming that it always corresponds to either a single core or a double core, and then determining whether it is a single core or a double core. The other method is a single core. The peak that can take both single core and double core is not always decided to be either, but "take both single core and double core". The abundance ratio of single core and double core shall be the same for all peaks that can take both.

Follow the procedure below.
The following describes the double core, but the idea is the same in the case of the multi-core.
i. Preparation Each of the peaks obtained in step 1 is divided into three types: a peak that can take only a single core, a peak that can take only a double core, and a peak that can take both a single core and a double core, and the abundance ratio of each is calculated. .. Of the peaks obtained in step 1, the abundance ratio of peaks that can only take single cores is "S (%)", the abundance ratio of peaks that can only take double cores is "D (%)", and single cores and double cores. The abundance ratio of peaks that can take both is defined as "S & D (%)".
Further, the abundance ratio of the single core obtained in step 3 is defined as "RS (%)", and the abundance ratio of the double core is defined as "RD (%)".

ii. When the value of "S" is smaller than the value of "RS" As an example
・ Existence ratio of peaks that can only be taken with a single core "S = 18 (%)",
・ Existence ratio of peaks that can only be taken by double core "D = 15 (%)",
・ Existence ratio of peaks that can take both single core and double core "S & D = 67 (%)"
-Calculated single core abundance ratio "RS = 25 (%)" obtained in step 3,
-Calculated double core abundance ratio "RD = 75 (%)"
And.
In this case, the peak with a single core is still RS-S = 25-18 = 7%.
Therefore, for all peaks that can take both single core and double core, each is divided into single core 7 vs. double core 60. That is, it is assumed that both the single core and the double core belong to one peak, the jingle core exists at the abundance ratio of 7/67, and the double core exists at the abundance ratio of 60/67.
According to this method, the peak ratio corresponding to the single core is 25%, and the peak ratio corresponding to the double core is 75%.

iii. When the value of "D" is smaller than the value of "RD" As an example
・ Existence ratio of peaks that can only be taken with a single core "S = 18 (%)",
・ Existence ratio of peaks that can only be taken by double core "D = 15 (%)",
・ Existence ratio of peaks that can take both single core and double core "S & D = 67 (%)"
-The calculated single core abundance ratio obtained in step 3 is "RS = 80 (%)",
・ Calculated double core abundance ratio is "RD = 20 (%)"
And.
In this case, the peak having a double core is still RD-D = 20-15 = 5%.
Therefore, for all peaks that can take both single core and double core, each is divided into single 62 vs. double 5. That is, it is assumed that both the single core and the double core belong to one peak, the jingle core exists at the abundance ratio of 62/67, and the double core exists at the abundance ratio of 5/67.
According to this method, the peak ratio corresponding to the single core is 25%, and the peak ratio corresponding to the double core is 75%.
The contents of steps 1 and 2 in FIG. 2 are the same as the contents of steps 1 and 2 in FIG.

(6) Step 4 (determination of side chain and cross-linking) (S4 in FIG. 1, S4 in FIG. 2)
In step 4, either the structure X or the structure Y specified in step 2 is adopted according to the determination in step 3, and the side chains and crosslinks are determined and assigned to the adopted core portion ( S4) in FIG.
Alternatively, as an alternative method, the structure X specified in step 2 is adopted for the single core and the structure Y specified in step 2 is adopted for the multi-core according to the determination in step 3 of FIG. Then, side chains and crosslinks are determined and assigned to the adopted core portion (S4 in FIG. 2).

(A) "Adopting either the structure X or the structure Y specified in step 2 according to the decision in step 3" is performed as follows.
In step 3 above, it was determined whether a peak corresponds to a single core or a double core. However, in step 2, both the optimum structure X in the case of a single core and the optimum structure Y in the case of a double core have been specified. As a result, the single core of structure X, which was optimized in step 2, was adopted for the peak that was "corresponding to a single core" in step 3, and the peak that was "corresponding to a double core" was selected for the peak. The double core of structure Y, which was optimized in step 2, has been adopted.
However, as described above, there are peaks in which there are molecules that can only have a single core structure in the peak group to which the double core is applicable. For such peaks, the single core of structure X is adopted. Will be done. The same is true in the opposite case.
In step 4 of FIG. 2 following step 3 (another method) of FIG. 2, it was determined that the peaks capable of taking both single core and double core take both single core and double core, respectively. In this case, the structure X specified in step 2 is adopted for the single core, and the structure Y specified in step 2 is adopted for the multi-core, and the determination is made.

(B) “Determining the side chain and cross-linking” is performed by the following procedures i to iii.
i. As described above, it was possible to identify whether the single core or the double core corresponds to each peak of the FT-ICR-mass spectrometry by steps 2 and 3. However, simply assuming the presence of only the core portion in these does not match the mass indicated by the m / z value of the peak obtained by FT-ICR-mass spectrometry for the target sample. That is, the total mass based on carbon, hydrogen, and heteroatoms involved in the formation of the core portion is different from the mass indicated by the m / z value of the peak obtained by FT-ICR-mass spectrometry. Occurs.
Therefore, it is considered that the difference in mass is derived from the existence of side chains bonded to the core and crosslinks connecting the cores, and the number of carbon and the number of hydrogen are calculated so that the difference is eliminated. Allocate it to the core species as side chains and crosslinks.
For example, suppose that a certain double core structure composed of "core 1-core 2" is assigned to a certain peak of m / z = n by the above procedure. At this time,
Difference in mass (d) = n- (mass of core 1 + mass of core 2)
Is derived from the presence of side chains and crosslinks.

ii. The above i. In, the number of carbons and the number of hydrogens to be allocated as side chains and crosslinks are obtained, but the structure of side chains and crosslinks has not yet been determined. Therefore, in estimating what kind of structure the side chains and crosslinks correspond to, for example, the following rules are determined in consideration of the existence probability of the expected combination of side chains and crosslinks, and according to the following rules. You can estimate it. As a rule, conditions such as the upper limit of the number of carbons constituting the side chains and crosslinks and the number of side chains may be set in advance.
iii. In the above i, when the side chain and the crosslink corresponding to the difference in mass do not exist, the structure that the core 1 and the core 2 are simply bonded may be applied.
(C) “Assigning the side chain and crosslink to the core” determined above includes determining which core and position of the single core or double core the side chain and crosslink are located. is not it.
(D) In this way, the core structure could be determined, and the side chains and crosslinks could be determined.

(7) Step 5 (optimization of molecular abundance ratio) (S5 in FIG. 1, S5 in FIG. 2)
Step 5 is a step of optimizing the abundance ratio of the molecule identified in step 1 by using the analysis information for the entire original multi-component mixture.
Specifically, the abundance ratio of each molecule specified in step 1 is adjusted so as to match the value of the average physical characteristic value measured for the entire multi-component mixture.
"Optimizing" does not only literally mean "finding the optimum value", but specifically, it is specified in step 1 so that the deviation from the average physical property value measured for the entire multi-component mixture becomes small. It means to broadly include the act of adjusting the abundance ratio of each molecule and refining it.

(A) "Analysis of the entire original multi-component mixture" refers to, for example, the following, but if the information to be considered is appropriately selected from the following i to iv according to the desired degree of optimization. Good.
i. Elemental analysis value By performing elemental analysis on a multi-component mixture, the hydrogen / carbon ratio, nitrogen / carbon ratio, sulfur / carbon ratio, and oxygen / carbon ratio can be found. In particular, it is preferable to pay attention to the hydrogen / carbon ratio.
ii. Aromaticity index (fa)
The aromaticity index (fa) refers to the ratio of carbon atoms involved in the formation of an aromatic ring among carbon atoms in a multi-component mixture, and is represented by fa = Ca / C.
iii. Hydrogen atom distribution Regarding the hydrogen atom in the multi-component mixture, its position (what kind of carbon atom is bonded to hydrogen, that is, hydrogen bonded to the carbon of the aromatic ring, is bonded to the carbon of the fatty chain It is information about what kind of hydrogen is hydrogen, what kind of aromatic ring and what position carbon is in the fat chain, etc.).
iv. Number average molecular weight

(B) “Optimization using analytical information for the entire original multi-component mixture” may be performed by, for example, the following method.
It was obtained from the abundance mole fraction of each molecule derived based on the above values such as hydrogen / carbon ratio, aromaticity index, hydrogen atom distribution, number average molecular weight, etc., and the FT-ICR mass spectrum of the multi-component mixture. This is a method of finding the correction coefficient so that the deviation from the mole fraction of each molecule derived from the intensity of each peak is minimized.

In this way, the molecular structure of each component constituting the multi-component mixture and the abundance ratio thereof can be specified by the above steps 1 to 4, and more preferably step 5.

In the present invention, the multi-component mixture may be one fraction obtained by fractionating a multi-component mixture into two or more arbitrary portions. That is, when the "multi-component mixture" in the above is regarded as one fraction I obtained by fractionating a large group of "multi-component mixture A", the "multi-component mixture A" is a fraction. It can be regarded as a mixture of as many fractions as there are fractions, such as I, Fraction II, and so on. For the fraction II, the molecular structure of each component constituting the fraction II can be specified by the same method as that used for the fraction I.

In performing the fractionation, the standard used as the boundary of the fractionated object or the method for fractionation is not particularly limited. Specifically, it is preferable to carry out by the following method.
This is a method in which a multi-component mixture is subjected to a highly accurate type-specific separation pretreatment and fractionated into a plurality of components. Especially in the case of heavy oil, it is preferable to carry out such fractionation. The method of "separation pretreatment by type" is not particularly limited and may be separated into several components according to an arbitrary standard. However, a column chromatography fractionation method, a Soxhlet extraction method or a high-speed solvent extraction method A known method such as a solvent extraction method such as the above may be used. In the case of heavy oil, it is preferable to use a column chromatographic fractionation method, for example, as in the method described in JP-A-2011-133363. The number of components to be fractionated may be appropriately selected according to the purpose.

Specifically, a method including the following first to fourth steps can be mentioned.
(First step)
The heavy oil is separated into marten, which is soluble in n-paraffin, and other insoluble components.
(Second step)
The malten content separated in the above (first step) is saturated using column chromatography (Sa), 1-ring aromatic component (1A), 2-cyclic aromatic component (2A), and 3 or more ring aromatic components (Sa). It separates into each fraction of 3A +), polar resin (Po) and polycyclic aromatic resin (PA).
(Third step)
More preferably, the three or more rings of the aromatic fraction (3A +) obtained in the second step are further subjected to preparative liquid chromatography to further obtain a Peri-type tetracyclic aromatic component and a Cata-type tetracyclic aromatic component. Fractions and, in some cases, 5 or more rings of aromatics (5A +) may be separated.

Next, a method of determining a composition model of a multi-component mixture using a computer will be described.
This is the molecule of each component constituting each fraction by the above-mentioned method for step A in which the multi-component mixture is fractionated into two or more arbitrary portions and each fraction fractioned in step A. Step B for specifying the structure and abundance ratio, and step C for integrating the molecular structure and abundance ratio of all the components obtained for all the fractions according to the mixing ratio of each fraction fractionated in step A. It is a method characterized by including.
As described above, the "multi-component mixture A" is regarded as a mixture of as many fractions as the number of fractions, such as fraction I, fraction II, etc. obtained by fractionating the mixture. With respect to the fraction, the molecular structure of each component constituting the fraction and its abundance ratio are specified by the above method. After that, if all the components of the total fraction are integrated according to the mixing ratios of the fraction I and the fraction II in the "multi-component mixture A", that is, the fraction yield, the "multi-component mixture" is obtained. It is possible to specify what kind of component and what proportion are composed of the entire composition model of "A".

Furthermore, the present invention is also a method of estimating the physical property value of the multi-component mixture based on the molecular structure of each component constituting the multi-component mixture and the abundance ratio thereof, which are specified by the above method.
Examples of the "physical characteristic value" referred to here include the following. Gibbs produced Free energy, ionization potential, polarization rate, dielectric constant, vapor pressure, liquid density, API degree, gas viscosity, liquid viscosity, surface tension, boiling point, critical temperature, critical pressure, critical volume, heat generated, heat capacity, bipolar Moment, enthalpy, entropy, etc.
These physical property values are usually calculated using the atomic group contribution method or the molecular orbital method. In the atomic group contribution method, when determining the physical property value of a substance, the chemical structure of the substance is specified, and the substance is based on the unique parameter values of various existing atomic groups, that is, "groups". It is a method of calculating the physical property value of. That is, it is premised that the "group" of the substance is specified. Also, in the molecular orbital method, it is premised that the "group" of the substance is first specified and the structure is specified based on it.
In the present invention, as described above, various atomic groups existing are specified for each component constituting the multi-component mixture. Therefore, the components are specified by using known and unique parameter values of the various atomic groups. It is possible to calculate the physical property value of. Further, since the abundance ratio of each component is also specified, if this abundance ratio is taken into consideration, it is possible to appropriately estimate the physical characteristic value of the entire multi-component mixture from the physical characteristic value of each component.

In the operation of a multi-component mixture, particularly a petroleum refinery, optimum conditions are usually set with the physical characteristic value of petroleum as a raw material as a guideline.
The present invention is a method of operating an apparatus relating to a multi-component mixture, particularly petroleum, characterized in that operating conditions are set based on the above-estimated physical property values of the multi-component mixture. "Based on physical characteristics" means
When the physical property values estimated by the above method are used alone or in combination of two or more as a direct factor for setting the operating conditions, or when the physical property values estimated by the above method are combined with other normal physical property values. It also includes cases where they are combined and become factors that determine operating conditions. Further, although the physical property value estimated by the above method is not a direct factor for determining the operating conditions, it also includes a wide range of cases where it is used as data for determining other operating factors.

Next, an embodiment of the present invention will be described in accordance with steps 1 to 5 using a hypothetical model for convenience in order to facilitate understanding of the invention. The "multi-component mixture" is modeled on a polycyclic aromatic resin (PA).
The following is merely a schematic simplification and explanation of the assumed model, and thus the present invention is not to be interpreted in a limited manner based on this.

(Points of this method)
The present invention is a method for specifying the molecular structure of each component constituting the multi-component mixture and its abundance ratio. Specifically, the target multi-component mixture is subjected to FT-ICR-mass spectrometry. For each of the peaks, the molecular structure of the molecule (there may be more than one) belonging to the peak is displayed by JACD and specified.
For example, suppose that a multi-component mixture is subjected to FT-ICR-mass spectrometry to obtain a mass spectrum. Many peaks are measured in this mass spectrum, and taking the peak with m / z of 522.24 as an example, "The molecule belonging to this peak has a molecular formula of C38H34S and corresponds to that molecular formula. The structure of one molecule is composed of core 1, core 2, cross-linking, and side chain as shown in FIG. 3 in JACD. " Then, when there are a plurality of JACDs corresponding to the molecular formula C38H34S, the structures of each of them are displayed and specified by JACDs.

Each step shown in the flowchart of FIG. 1 will be described by applying it to the assumed model.
(1) Step 1 (mass spectrometry) (S1 in FIG. 1)
In step 1, mass spectrometry is performed on the multi-component mixture, the molecular formulas of the molecules belonging to each peak are specified for all the peaks obtained by the mass spectrometry, and the abundance ratio of the molecules corresponding to the molecular formulas is further specified. .. In other words, the molecular formula of each component constituting the multi-component mixture and the abundance ratio of the molecule corresponding to the molecular formula are specified.
In the mass spectrum obtained by FT-ICR-mass spectrometry, the mass can be measured extremely accurately, so that the molecular formula of the molecule belonging to each peak can be specified.
For example, looking at the chart of FIG. 3, many peaks appear in the vicinity of mass (m / z) of 303.2, and the molecular formula of the molecule to which they belong can be accurately specified for each of them.
In addition, the ratio of the height of a certain peak to the total height of all peaks represents the abundance ratio of molecules belonging to the peak.

(2) Step 2 (Specification of the structure of the core part of the molecule) (S2 in FIG. 1)
In step 2, the molecule belonging to each of the peaks obtained in the mass spectrometry of step 1 is the optimum structure X when it is assumed to be a single core, and its optimum structure Y when it is assumed to be multi-core. Identify both.
(A) First, the core portions of the molecule belonging to each peak are listed by the following procedures i to iii.
i. For each peak obtained from FT-ICR-mass spectrometry, the molecular formula of the molecule assigned to that peak is determined.
As a result, information such as the type and number of heteroatoms in the molecular formula and the DBE value can be obtained.
ii. Based on the type and number of heteroatoms and the DBE value, all corresponding cores are listed.
In this enumeration, the type and number of heteroatoms and the DBE value are collated from the "core structure list", and all the cores considered to be applicable are selected from the list.
For example, if the molecular formula of a certain peak is "C30H18", this peak becomes "heteroatom = none, DBE value = 22".

iii. Selection from the core structure list Single cores and double cores (combination of cores with a sum of DBE values of 22) with "heteroatom = none, DBE value = 22" are set as shown in (1) and (2) below. Then select from the core structure list.
(1) The following two cores A and B were selected from the core structure list as a single core with a DBE value of 22.

(2) As the double core, the following three sets of double core C, double core D, and double core E were selected from the core structure list.
Double core C (DBE value = 10 + 12)

Double core D (DBE value = 7 + 15)

Double core E (DBE value = 8 + 14)

(B) Next, among the single cores A and B listed above and the double cores C, D, and E, the most appropriate candidate for the core of the peak is the single core, according to the following i and ii. Identify one double core each.
i. Of the two single cores A and B listed above, the one with the smallest number of hydrogens attached to the aromatic ring of the core is specified as the most appropriate one.
Comparing core A and core B in the above model, core B is identified as the most appropriate because it has a smaller number of hydrogens attached to the aromatic ring of the core.

ii. Of the three sets of double cores C, D, and E listed above, first, in each set of double cores, the set with the smallest number of hydrogens bonded to the aromatic ring of one of the cores forming the double core is selected. Select as the most reasonable one. If one cannot be determined by this method, the one with the smallest difference in the number of hydrogens bonded to the aromatic rings of the two cores forming each of the multiple candidate double cores is the most appropriate one. Identify as.
Comparing the above double core C, double core D, and double core E, the number of hydrogens bonded to the aromatic ring of one core of the double core E is the smallest, so that the double core E is specified as the most appropriate one. ..

The above-mentioned core species enumeration and selection are performed for all peaks.

(3) Step 3 (determination of single core or double core) (S3 in FIG. 1)
In step 3, it is determined whether the molecule belonging to each of the peaks obtained by the mass spectrometry in step 1 is a single core or a double core.
In this step, first, for each of the peaks obtained by FT-ICR-mass spectrometry, it is assumed that the molecule assigned to each peak corresponds to either single core or double core, and then single. Determine whether it is a core or a double core. Follow the procedure i to iv below.
i. For all the peaks obtained by FT-ICR-mass spectrometry, the abundance ratio of each of the single core and the double core is determined.
The "unit structure" of a sample can be estimated by performing proton NMR analysis and elemental analysis on the sample. If the unit structure can be estimated, the molecular weight of that structure can also be estimated.
In the sample, the "unit structure" was specified as follows from the results of proton NMR analysis and elemental analysis. The molecular weight is 318.

On the other hand, the average molecular weight of the sample was determined by a known method and found to be 353.
At this time, P value (degree of polymerization) = "average molecular weight" / "molecular weight of basic skeleton"
= 347/318
= 1.09
Therefore, the abundance ratio of the dimer (“P value -1”) is 1.09-1 = 0.01, that is, 9%.
This value is interpreted as corresponding to the "double core abundance ratio" as explained above.

ii. Next, at the abundance ratio (91%: 9%) of the single core and the double core obtained in i above, all the peaks obtained by the original FT-ICR-mass spectrometry are classified.
That is, in all the peaks obtained by the original FT-ICR-mass spectrometry, the peaks are arranged in order from the one with the smallest m / z value, and the peak intensities are added up from the one with the smallest m / z value. Then, a line is drawn and classified when the ratio of the total value to the total intensity of all peaks becomes the above-mentioned "presence ratio of single core and double core (91%: 9%)".
Of those classified in this way, the one with the smaller m / z value corresponds to the single core, and the one with the larger m / z value corresponds to the double core.
However, even in the peak group to which the double core is applicable, there are peaks that can only have a single core structure due to the structure such as the DBE value and the number of heteroatoms. These are treated as a single core. That is, conversely, there are peaks that can only have a double-core structure even in the peak group to which a single core is applicable. These are treated as double cores.

iii. From the above, it is determined whether each peak by FT-ICR-mass spectrometry corresponds to a single core or a double core.
FIG. 5 shows that a single core corresponds to a peak having m / z smaller than about 720, and a double core corresponds to a peak having m / z greater than about 720. However, in reality, some of the peaks that double cores correspond to can only be single cores due to their structure. These are treated as a single core.
If some of the molecules attributed to the peak can only have a single core or only a double core, it is preferable to adjust the determination of single core or multi-core by the method described above.

(4) Step 4 (determination of side chain and cross-linking) (S4 in FIG. 1)
In step 4, either the structure X or the structure Y specified in step 2 is adopted according to the determination in step 3, and the side chains and crosslinks are determined and assigned to the adopted core portion. ..
Step 4 is performed according to the following procedure.
i. In step 3, it was determined whether the single core was applicable or the double core was applicable for all peaks, while in step 2, the single core 1 that was most appropriate for each peak was determined. Species and one double core were identified and assigned.
Therefore, for the peak to which the single core is applicable, the core part of the specified single core is determined as "the core part of the molecule belonging to the peak", and for the peak to which the double core is applicable, , The identified core portion of the double core will be determined as the "core portion of the molecule belonging to that peak".

ii. The sum of the masses based on carbon, hydrogen and heteroatoms involved in the formation of the core part identified above also differs from the m / z value at the peak measured by the FT-ICR-MS. ..
It is considered that this difference is derived from the existence of side chains bonded to the core and crosslinks connecting the cores, and the number of carbon and the number of hydrogen are calculated so that the difference is eliminated, and the side chains are used. Allocate to the core as chains and crosslinks.
For example, it is assumed that the following double core E is specified for a peak of m / z = 438.2.

At this time, the difference (d) is expressed by the following equation (3).
(D) = m / z value − (mass of double core E) ・ ・ ・ (3)
Substituting the mass of the double core E into this equation (3),
(D) = 438.2- (168.09 + 242.11) = 28
This difference is derived from the presence of side chains and crosslinks.
Here, considering that the value "28" is derived from two "-CH2-", the side chain and the crosslink are present in the double core E.
Therefore, in estimating what kind of structure the side chain and crosslink correspond to, the number of carbons and hydrogens to be allocated is estimated according to an appropriate rule for convenience of calculation.
For example, the following rules may be appropriately determined.
Rule 1: Up to a value X with a mass difference (d), it is assumed that there is no side chain and it is derived only from cross-linking.
Rule 2: If the mass difference (d) exceeds a certain value X, the crosslink is allocated in Rule 1 and then allocated to the side chain. A rule may be set for the maximum number of carbon atoms that can be taken per side chain, and allocation may be made accordingly.

In summary, by the above steps 1 to 5, the molecular structure of each component constituting the multi-component mixture can be specified by JACD, and the abundance ratio thereof can be specified.

(5) Step 5 (optimization of molecular abundance ratio) (S5 in FIG. 1)
In step 5, the abundance ratio of each component specified in step 1 is optimized by using the analysis information for the entire original multi-component mixture.
Here, we will focus on the hydrogen / carbon atom ratio and show a method for correcting the peak intensity.
In general, the decrease in peak sensitivity in mass spectrometry is remarkable in the case of a molecule having a large molecular weight, and the sensitivity decreases as the molecular weight increases. Specifically, after fractionation, fractions with a large molecular weight tend to be observed with a low abundance of molecules with high aromaticity, that is, a high hydrogen / carbon atom ratio. Therefore, the hydrogen / carbon atom ratio estimated from the mass spectrometry result is observed to be smaller than the value obtained from the elemental analysis result of the fractionation component.

In order to correct this effect, it is necessary to correct the sensitivity of mass spectrometry. The procedure is generally as follows.
(A) Let Mc be the molecular weight at which the decrease in sensitivity begins, Mi be the molecular weight of each peak, Ii be the peak intensity of the peak, and bi be the sensitivity correction coefficient. Here, the peak intensities are standardized so that the total of all peak intensities is 100%.
(A) For the molecule of Mi ≦ Mc, set bi = 1.
Further, in the region where Mi exceeds Mc, it is assumed that bi increases linearly with an increase in molecular weight.
The above assumptions can be summarized as follows.
・ In Mi ≤ Mc, bi = 1
-When Mi> Mc, bi = a · fi · (Mi-Mc)
(A is the rate of change of bi with respect to the molecular weight, and fi is the peak sensitivity of peak i.)
(C) When the above sensitivity correction coefficient is used, the carbon number (Cm) and hydrogen number (Hm) of the sample used for mass spectrometry can be obtained.
From this value, the H / C atomic ratio of the sample is calculated as Hm / Cm.
(D) If the sensitivity of mass spectrometry is equal for all peaks, the H / C atomic ratio measured by elemental analysis and Hm / Cm calculated by mass spectrometry should be equal, so the difference between the two is d. and when,
(H / C bars represent hydrogen / carbon atoms obtained by elemental analysis.)
Is the optimum solution. Therefore, a and Mc are determined so that d ² is minimized.
(E) After determining a and Mc, the intensities of all peaks are corrected by bi.
(F) After correction, the peak intensities are standardized again so that the total of all peak intensities is 100%.

As described above, the molecular structure of each component constituting the multi-component mixture and the abundance ratio thereof could be specified by steps 1 to 6.

Next, an example will be described in the case where the multi-component mixture is subjected to type-specific separation pretreatment.
I. Fractionation by type As a sample, vacuum residual oil (VR) obtained by distillation of atmospheric residual oil under reduced pressure was used. Decompressed residual oil (VR) corresponds to heavy oil. Saturated components (Sa), 1-ring aromatics (1A), 2-cyclic aromatics (2A), obtained by performing the pretreatment method (steps 1 to 3) on the vacuum residual oil (VR), About each fraction of 3 or more rings of aromatic (3A +), polar resin (Po) and polycyclic aromatic resin (PA), and each fraction of asphaltene (As) separated from marten in the first step. , The profit rate of each was calculated.

The first and second steps of the pretreatment method were carried out by the following methods.
<First step: Separation of marten>
7 g of the sample was weighed in an Erlenmeyer flask having a capacity of 500 ml, 220 ml of n-heptane was added, an air cooling tube was attached, and the mixture was boiled at reflux for 1 hour in an n-heptane insoluble matter tester.
After reflux boiling, the mixture was left to cool and the asphaltene content was separated using a filter paper to obtain a fraction containing the marten content.
<Second step: separation by column chromatography maltene fraction>
The marten content obtained in the first step was separated by column chromatography under the following conditions.
(1) Column conditions for column chromatography Column: 15 mm x 600 mm (gel-filled part, made of glass)
Gel: Silica gel 40g + Alumina gel 50g (after activation)
Silica gel: Chromato Gel Grade 923AR, manufactured by Fuji Silysia
Alumina gel: Made by MP BiomebicaLs, MP Alumina, Activated, Neutral, Super I
Activation conditions: Silica gel 250 ° C. x 20 h, Alumina gel 400 ° C. x 20 h, 0.2 kg / cm ² (N ₂ gas) Pressurized Sample amount: 1.5 g (Marten)

(2) Separation method The following solvents were sequentially added to the column, and the elution solution was separated.
(I) Add 200 ml of n-heptane, and cut up to 250 ml of the eluted sample solution as the saturated component (Fr. Sa).
(Ii) 250 ml of a mixed solvent of 95% n-heptane and 5% toluene is added, and up to 200 ml of the eluted sample solution is cut as a single ring aromatic component (Fr.1A).
(Iii) Add 250 ml of a mixed solvent of 90% n-heptane and 10% toluene, and cut up to 200 ml of the eluted sample solution to obtain a bicyclic aromatic component (Fr.2A).
(Iv) Add 250 ml of toluene and cut 300 ml of the eluted sample solution to obtain 3 or more rings of aromatics (Fr.3A +).
(V) Add 250 ml of ethanol and cut 230 ml of the eluted sample solution to obtain a polar resin (Fr. Po).
(Vi) Add 100 ml of chloroform, then add 100 ml of (vii) ethanol, and repeat (vi) and (vii) again. (Vi) and (vii) are all separated as one fraction to obtain a polycyclic aromatic resin (Fr.PA).

The results were as follows.
Saturation (Sa) 10%, 1-ring aromatic (1A) 11%, 2-cyclic aromatic (2A) 8%, 3 or more aromatics (3A +) 35%, polar resin (Po) 9 %, Polycyclic aromatic resin (PA) 16%, and asphaltene (As) 11%.

II. Molecular structure identification
(1) Step 1
Mass spectrometry was performed on the sample using a mass spectrometer using the Fourier transform ion cyclotron resonance method, and for the peaks obtained by this, the molecular formulas of the molecules belonging to each of the 89 peaks were identified, and all the molecules corresponding to the molecular formulas were identified. The total abundance ratio was identified.
The details are as follows.
(A) A Fourier transform ion cyclotron resonance type solariX FT-ICR-mass spectrometer (manufactured by Bruker Daltoniks) equipped with a 12T (Tesla) superconducting magnet was used.
The measurement conditions are as follows.
-Sample used: Polycyclic aromatic resin (PA) obtained by the above type fractionation.
-Sample preparation method: Dissolve several tens of milligrams of the sample in chloroform, add about 1 μliter to a MALDI (matrix-assisted laser desorption / ionization) plate, and use the sample as a measurement sample after solvent evaporation.
-Ionization method: Laser desorption / ionization method (LDI method) (number of shots: 2000, oscillation frequency: 1000 Hz, power: 23%) was used.
As a result of the measurement, the mass spectrum shown in FIG. 6 was obtained.
(A) For each peak of the above mass spectrum, the specified molecular formula and abundance ratio (expressed in mole fraction) are as shown in Table 2 below.
The number of peaks is 2117. Only a part of them (peak numbers 11 to 2109 are omitted) are shown below. In the table, peak numbers are assigned in order from the peak with the smallest m / z value.

(2) Step 2
Both the optimum structure X when the molecule belonging to each of the peaks obtained in the mass spectrometry in step 1 was assumed to be a single core and the optimum structure Y when it was assumed to be a multi-core were identified.
The details are as follows.
(A) For each peak obtained in step 1, the heteroatom species, number and DBE value are obtained from the molecular formula, and all the single cores and double cores corresponding to the heteroatom species, number and DBE value are obtained. It was picked up from the core structure list created in advance.
(B) Furthermore, the most appropriate one was selected from the single core and double core picked up above.
(C) Some of all peaks are shown below.
Since the above (a) and (b) are processed on the computer, the result of (a) cannot be taken out and shown.

(3) Step 3
It was determined whether the molecule attributed to each of the peaks obtained by mass spectrometry in step 1 was single-core or multi-core.
The details are as follows.
(A) In the sample, the "unit structure" was specified from the results of proton NMR analysis and elemental analysis, and the P value (degree of polymerization) was obtained from the following formula.
P value (degree of polymerization) = "average molecular weight" / "molecular weight of unit structure" = 1.09
Therefore, the abundance ratio of the dimer (“D value -1”) was 1.09-1 = 0.09, that is, 9%.
This corresponds to the "double core abundance ratio" as explained above.
(B) From the above, the abundance ratio of single core and double core (91%: 9%) was determined. Therefore, for convenience, the original FT-ICR-mass spectrometry peak is shown in FIG. And double core.
(C) Since one single core type and one double core type have already been specified and assigned to each peak, the specified single core is the "core of the peak" for the peak consisting of a single core. For the peak consisting of double cores, the specified double core was determined as "the core of the peak".
However, even in the m / z group consisting of the above double cores, there are molecules that can have only a single core structure. These are treated as a single core.

(4) Step 4
In response to the determination in step 3, either the structure X or the structure Y specified in step 2 was adopted, and side chains and crosslinks were determined and assigned to the adopted core portion.
Since step 4 is a process processed by a computer, the result cannot be retrieved in the middle.

(5) Specification of molecular structure with respect to the mass spectrum of the sample The molecular structure of each of the peaks obtained in step 1 above was specified as shown in Table 3.
(A) Peak numbers are assigned so as to correspond to the peak numbers in Table 2 shown in step 1.
(A) The molecular formula of peak number 1 is "C21H21N", and the structure of this molecule is indicated by JACD using alphanumeric characters.

(C) In the above table, in order to convert the JACD display using alphanumeric characters into the structure of the core, the bridge, and the side chain, a code table for rereading the alphanumeric character information into the structural information may be created. For example, the table below.

(D) Using this table, the molecular structure of the molecular formula "C21H21N" is as follows.
i. Since the core 1 is "022009", it has the following structure.
ii. Since core 2 and core 3 are "000000", it means that they do not exist.
iii. Since the bridge 1 and the bridge 2 are "000000", it means that they do not exist.

iv. Since the side chain 1 is "0SC004", it has the following structure.
v. In this way, the structure of the molecule of the molecular formula "C21H21N" could be displayed and specified by JACD.
(E) In the same way, the structures of all the molecules could be displayed and identified by JACD.

III. Data integration of each fraction
(1) Saturation (Sa), 1-ring aromatic (1A), 2-cyclic aromatic (2A), 3 or more aromatics (3A +), polar resin (Po) and asphaltene (As) The molecular structure of the polycyclic aromatic resin was specified by the same method as that used for the polycyclic aromatic resin, except that the following was changed.
(A) Regarding the ionization method for saturated components, 1-ring aromatics, 2-cyclic aromatics, 3 or more aromatics, and polar resins, atmospheric pressure photoionization (APPI method) (sample flow velocity 200 μL / h, The ion accumulation time was 0.2 sec., And the number of integrations was 100 times).
(A) As the ionization method for asphaltene, a laser desorption / ionization method (LDI method) (number of shots: 5000, oscillation frequency: 1000 Hz, power: 17%) was used.

(2) Integration of all fractions Saturated components (Sa), monocyclic aromatics (1A), bicyclic aromatics (2A), aromatics with 3 or more rings (3A +), polar resins (Po) ), Polycyclic aromatic resin (PA) and asphaltene (As), the molecular structure and abundance of all components are integrated for all fractions according to the respective gains (presence ratios) obtained above. did.
(3) From the above, it was possible to specify the molecular structure and abundance ratio of all the molecules constituting the reduced pressure residual oil (VR) with respect to the sample reduced pressure residual oil (VR).

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the present invention. In the above-described embodiment, FT-ICR-mass spectrometry is used as the mass spectrometry, but in the present invention, the mass spectrometry is not limited to this.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the present invention. In the above-described embodiment, FT-ICR-MS is used as the mass spectrometry, but the mass spectrometry is not limited to this.

According to the present invention, since the structure of the molecules constituting the petroleum can be specified, it can be widely applied in the analysis of various reactions of petroleum at the molecular level. Furthermore, such analysis at the molecular level contributes to dramatically improving the operational stability and operational efficiency of petroleum refining facilities.

Claims (12)

A method of identifying the molecular structure of each component and its abundance ratio with respect to a multi-component mixture using a computer.
In step 1, mass spectrometry is performed on the multi-component mixture, the molecular formula of the molecule belonging to the peak is specified for each of the obtained peaks, and the abundance ratio of the molecule is further specified.
Both the optimum structure X when the molecule belonging to each of the peaks obtained in the mass spectrometry in step 1 is single core and the optimum structure Y when it is multi-core are specified. Step 2 and
Step 3 for determining whether the molecule belonging to each of the peaks obtained by the mass spectrometry in step 1 is single-core or multi-core, and
In response to the determination in step 3, either the structure X or the structure Y specified in step 2 is adopted, and the side chain and the crosslink are determined and assigned to the adopted core portion. A method characterized by inclusion. A method of identifying the molecular structure of each component and its abundance ratio with respect to a multi-component mixture using a computer.
In step 1, mass spectrometry is performed on the multi-component mixture, the molecular formula of the molecule belonging to the peak is specified for each of the obtained peaks, and the abundance ratio of the molecule is further specified.
Both the optimum structure X when the molecule belonging to each of the peaks obtained in the mass spectrometry in step 1 is single core and the optimum structure Y when it is multi-core are specified. Step 2 and
In the peak obtained by the mass spectrometry in step 1, the peaks that can take both single core and multi-core are assumed to take both single core and multi-core, respectively, and the abundance ratio of single core and multi-core in the peak is determined. Step 3 and
In response to the determination in step 3, the structure X specified in step 2 is adopted for the single core, and the structure Y specified in step 2 is adopted for the multi-core, and the adopted core portion is used. On the other hand, a method comprising the step 4 of determining and allocating side chains and crosslinks. The invention according to claim 1 or 2, further comprising step 5 of optimizing the abundance ratio of each component specified in step 1 by using analytical information for the entire original multi-component mixture. Method. In identifying the single-core or multi-core structure in step 2, the information on the cores obtained in steps 1 and / or step 2 is collated with the information on the cores described in the core structure list prepared in advance. The method according to any one of claims 1 to 3, wherein the structure of a single core or a multi-core is specified. The method according to any one of claims 1 to 4, wherein the core structure list is a list of various cores that can be assumed to constitute each component constituting the multi-component mixture. The invention according to any one of claims 1 to 5, wherein the molecular structure of each component constituting the multi-component mixture is represented by the type of attributes including cores, side chains and crosslinks, and the number of attributes. Method. The method according to any one of claims 1 to 6, wherein the multi-component mixture is one fraction obtained by fractionating a multi-component mixture into two or more arbitrary portions. .. A method of determining a composition model of a multi-component mixture using a computer.
Step A to fractionate the multi-component mixture into two or more arbitrary parts,
Step B and the above-mentioned step B for specifying the molecular structure and abundance ratio of each component constituting each fraction by the method according to any one of claims 1 to 5 for each fraction fractionated in step A. A method comprising: step C, which integrates the molecular structure and abundance ratio of all components obtained for all fractions according to the mixing ratio of each fraction fractionated in step A. A method for estimating a physical property value of a multi-component mixture based on the molecular structure of each component constituting the multi-component mixture and the abundance ratio thereof, which is specified by the method according to any one of claims 1 to 7. A method of operating an apparatus for a multi-component mixture, which comprises setting operating conditions based on the physical property values of the multi-component mixture estimated by the method according to claim 9. The method according to any one of claims 1 to 10, wherein the multi-component mixture is petroleum. A computer program for executing the method according to any one of claims 1 to 9.