JP7184522B2 - Methods for estimating properties of multicomponent mixtures - Google Patents

Description

The present invention relates to a method for estimating properties of multicomponent mixtures. More specifically, the present invention uses a computer to specify the molecular structure of each component that constitutes a multicomponent mixture, and based on the structural information obtained therefrom and a new multicomponent aggregation model using a physical property value database, multiple It relates to a method for quantitatively estimating properties such as dissolution, aggregation and precipitation of each component in various multi-component mixtures including crude oil, an apparatus used therein, and a computer program that causes a computer to execute the method or apparatus. .

In the operation of petroleum refining equipment, raw material oil is usually analyzed based on overall physical properties such as specific gravity, viscosity, and distillation properties (boiling point), and past operating results of oil types with similar data are analyzed. A method of determining the operating conditions with reference to the data is adopted.
However, these days, the types of imported crude oil are diversifying, and it is not easy to find similar past data. Furthermore, from the standpoint of improving operating efficiency and protecting the environment, it is no longer enough to simply follow past operating results.
Therefore, instead of looking at the oil as a whole, such as its specific gravity, viscosity, and distillation properties, we should grasp the chemical structure and abundance ratio at the level of the hydrocarbon molecules that make up the oil. It has been thought that efficient operation based on more objectivity can be achieved if operating conditions can be set based on knowledge such as estimated physical property values. Therefore, in the petroleum industry, the advent of a technique for grasping petroleum at the molecular level has been eagerly awaited.
However, petroleum is a mixture of a huge number of hydrocarbon molecules, and heavy oil in particular has a large number of molecules with large molecular weights and complex chemical structures. It was very difficult to specify the chemical structure and also specify the abundance ratio of each of them.

Until now, when analyzing petroleum at the molecular level and analyzing the chemical structure, a high-resolution mass spectrometer, a Fourier transform ion cyclotron resonance mass spectrometer, has been used to measure the molecular weight with high precision. rice field. For example, it is the method described in Patent Document 1 or Patent Document 2.
In particular, in Patent Document 2, by colliding molecules that make up petroleum with argon or the like, the cross-linked portions in the molecules are cut and decomposed into core portions that are composed, and their chemical structures are determined. A method for estimating the molecular structure is described in which these are later combined to reconstruct the original molecule.

In addition, in the treatment of heavy oil containing a large amount of residue components such as asphalt, it is required to reduce the amount of residue as much as possible to improve the utilization rate of crude oil. In the process of petroleum refining, it is necessary to alleviate and suppress aggregation of asphaltenes, which are precursors of coke, in various situations including cracking of heavy oil. For this reason, it is common practice to pre-mix a solvent (solvent) with the raw material oil to alleviate or suppress the aggregation of asphaltenes. However, it is currently selected empirically.

On the other hand, the inventors of the present application conducted intensive research on techniques for suppressing and mitigating the aggregation of asphaltenes contained in heavy oil, and found that the difference in the Hansen solubility index values (Δδ) between asphaltenes and solvents and that of asphaltenes We found that there is a certain relationship between the degree of agglomeration and the degree of agglomeration, and developed a method of selecting a solvent using the difference (Δδ) as an index. Such a selection method is described in Patent Document 3 below.

Japanese translation of PCT publication No. 2014-500506 Japanese Patent Publication No. 2014-503816 JP 2014-218643 A

However, in the method described in Patent Document 2, which parts and which parts are selected and combined to construct a molecule are determined based on probability for the parts such as the core, crosslinks, and side chains that form the molecule. That's what it means. Therefore, even if the construction work of the molecular structure of the component was carried out in the same process based on certain mass spectrometry data, the obtained results would be different each time the construction work was carried out. That is, the method described in Patent Literature 2 has a fatal defect that the consistency and reproducibility of the obtained results cannot be ensured, and that "the operation stability of the apparatus cannot be ensured."

In addition, in heavy oil mixed with a solvent, the Hansen Solubility Index value of the liquid phase is considered to be determined based on the value of the solvent and the values of the liquid phase components in the heavy oil, not the value of the solvent itself. . For this reason, which of the components contained in heavy oil dissolves to form the liquid phase, how does the Hansen solubility index value of the liquid phase change, and as a result, which components aggregate or It is important to grasp whether it precipitates or not. However, the properties of the liquid phase, aggregate phase and solid phase of multi-component mixtures, which are solutions consisting of multiple components, the mechanism of phase change, especially the behavior of dissolution, aggregation and precipitation of asphaltenes in heavy oil, have not been studied by industry. Although it is a big theme, it is hardly elucidated.

The present invention has been made under such circumstances, and uses a computer to specify the molecular structure and abundance ratio of each component that constitutes a multi-component mixture with a certain degree of certainty, and the structural information and physical property values obtained therefrom. The purpose of this study is to provide a method for estimating the properties of each component in a multicomponent mixture based on a multicomponent aggregation model using a database. A further object of the present invention is to provide an apparatus and a program used in the method for estimating properties of the multicomponent mixture.

In order to achieve the above objects, the present inventors created the following inventions. That is, the method for estimating properties of a multi-component mixture according to the present invention is a method for estimating properties of a multi-component mixture by computer,
(1) performing mass spectrometry on the multi-component mixture, identifying the molecular formula of the molecule assigned to each peak obtained by performing mass spectrometry, and further identifying the abundance ratio of the molecule;
(5) for each molecule whose molecular formula has been specified in step (1), determine the structure of the core that constitutes them, and further determine and assign side chains and crosslinks;
(6) obtaining the melting point and Hansen Solubility Index value of each component from the molecular structure of each component of the multi-component mixture identified in steps (1) and (5);
(7) Among the components constituting the multi-component mixture, classify the component having a melting point lower than the desired temperature as a liquid phase component, and classify the component having a melting point equal to or higher than the desired temperature as a non-liquid phase component. a step;
(8) calculating an average Hansen Solubility Index value for the entire liquid phase as a weighted average value obtained by weighting the Hansen Solubility Index values of each component classified as the liquid phase component by the fraction of each component in the liquid phase; ,
(9) calculating the difference between the average Hansen Solubility Index value for the entire liquid phase and the Hansen Solubility Index value for each component in the non-liquid phase components;
(10) Each component in the non-liquid phase component is reclassified as a liquid phase component or a non-liquid phase component based on the difference, and each component reclassified as a liquid phase component is changed from the non-liquid phase component to the liquid phase component. to update the liquid phase component and the non-liquid phase component;
(11) Calculate the average Hansen solubility index value of the entire liquid phase after updating as a weighted average value obtained by weighting the Hansen solubility index value of each component in the liquid phase component after updating by the fraction of each component in the liquid phase. a step;
(12) repeating steps (9) to (11) until a final stage where no non-liquid phase components are reclassified as liquid phase components in step (10);
It is characterized by

In another embodiment of the present invention, a method for estimating physical property values of a multi-component mixture using the method for estimating properties of a multi-component mixture, a method for processing a multi-component mixture, an apparatus for estimating properties of a multi-component mixture, and A method of operating the apparatus, as well as a method of estimating properties of a multi-component mixture and a computer program for executing the apparatus are also provided.

In the method for processing a multicomponent mixture of the present invention, the properties of the original multicomponent mixture are estimated by the method for estimating properties of the multicomponent mixture described above, and the desired type of When the solvent is mixed in the desired fraction, when the temperature of the original multicomponent mixture is changed to the desired temperature, or when the original multicomponent mixture is mixed with the desired type of solvent in the desired fraction and the original multicomponent mixture Predict the properties of the new multicomponent mixture when the temperature is changed to the desired temperature, and based on the prediction, mix the desired type of solvent in the desired fraction into the original multicomponent mixture, or changing the temperature of the multi-component mixture to its desired temperature, or mixing the desired type of solvent in its desired fraction into the original multi-component mixture and changing the temperature of the original multi-component mixture to its desired temperature; It is characterized by

According to the method for treating a multi-component mixture of the present invention, it is possible to predict the properties of the multi-component mixture when a solvent is mixed with the multi-component mixture or the temperature of the multi-component mixture is changed. Based on this, it is possible to process multi-component mixtures.

Also, in the method of treating a multi-component mixture of the present invention, the desired type of solvent and its desired fraction, and/or its desired temperature are preferably Solvent and fraction in which all or part of the aggregated phase components and solid phase components in the original multicomponent mixture are dissolved, or the aggregation or precipitation of the aggregated phase components and solid phase components is suppressed, and / or temperature.

Accordingly, measures are taken to appropriately select the solvent species, add new solvents, or change the temperature of the solution to dissolve all or part of the aggregated and solid phases in the solution, or to dissolve the solute. can suppress aggregation or precipitation of

According to the present invention, a computer is used to specify the molecular structure and abundance ratio of each component that constitutes a multi-component mixture with a certain degree of certainty, and multi-component using physical property data linked to the structural information obtained therefrom. Component aggregation models can provide a way of estimating the properties of multicomponent mixtures.

4 is a flow chart illustrating a method according to an embodiment of the invention; FIG. 3 is a schematic diagram for explaining collision-induced dissociation; It is a mass spectrum obtained by FT-ICR-mass spectrometry and an example of JACD display of molecules attributed to a certain peak. It is a mass spectrum chart obtained by FT-ICR-mass spectrometry. FIG. 3 is a schematic diagram for explaining comparison and collation between m/z of peaks obtained in FT-ICR-mass spectrometry after collision-induced dissociation and accurate masses in the core structure list. The upper row is a chart of the mass spectrum obtained by FT-ICR-mass spectrometry for the sample multi-component mixture. It is a chart divided into “groups” for each and further peaked by the DBE value in the “groups” FIG. 3 is a schematic diagram for explaining the existence ratio of multi-cores; FIG. 4 is a schematic diagram for explaining the existence ratio of single cores; FIG. 4 is a schematic diagram of a core derived from a DBE value of 22; FIG. 4 is a schematic diagram of a core derived from a DBE value of 20; FIG. 4 is a schematic diagram for explaining “class” division of cores for each DBE value; FIG. 10 is a schematic diagram showing the “classes” of cores for each DBE value, arranged in descending parent mass order. FIG. 13 is a schematic diagram for explaining allocation of cores in FIG. 12; 1 is a mass spectrum chart obtained by FT-ICR-mass spectrometry for a polycyclic aromatic resin (PA). 1 is a mass spectrum chart obtained by FT-ICR-mass spectrometry after collision-induced dissociation for a polycyclic aromatic resin (PA). It is a schematic diagram of an HSP value. 1 is a graph showing the amounts of liquid, aggregated and solid phases and the average degree of aggregation of the aggregated phases of a model heavy oil without solvent. 1 is a graph showing the amounts of liquid, aggregated and solid phases and the average degree of aggregation of the aggregated phases of a model heavy oil in toluene solvent. 1 is a functional block diagram of an apparatus for estimating properties of a multi-component mixture according to an embodiment of the present invention; FIG. 1 is a graph showing the amounts of liquid, aggregate and solid phases and the average degree of aggregation of aggregated phases of a model heavy oil in equal mass mixed solvents of toluene and bromobenzene. 1 is a functional block diagram of an apparatus for estimating properties of a multi-component mixture according to an embodiment of the present invention; FIG.

<Definition>
Before describing the embodiments of the present invention, terms and expressions used in this specification will be described.
(1) "multi-component mixture"
A "multi-component mixture" is a concept encompassing all mixtures consisting of two or more components. The content ratio of the components is irrelevant. Specifically, it is preferably "petroleum", more preferably "heavy oil". More specifically, it is a "mixture containing many aromatic compounds as main components".

(2) "Component"
"Component" means "mass of a mixture based on specific physical or chemical properties", that is, "fractions (fractions) based on specific physical or chemical properties" )” means. As a method of grouping based on specific physical or chemical properties, for example, a method of specifying a boiling point range in a distillation test and fractionating substances within that temperature range as one component can be mentioned. In this case, the mixture is an "aggregate of fractions". Alternatively, a "component" may be regarded as an "aggregate of molecules recognized as belonging to the same molecular species", each of which constitutes a multi-component mixture. Here, "identical" means "identical after specifying the molecular structure completely", or "isomers on the molecular structure (same molecular formula but different structure) For example, it may be interpreted as meaning "having the same structure specified by a system such as JACD" described later. Furthermore, it can also be interpreted broadly as meaning "an aggregate of molecules grouped together based on an arbitrary standard."

(3) "Configure"
"Constituting a multi-component mixture" may not assume 100% of all components present in the multi-component mixture. Depending on how the molecular structure of each component specified by the present invention is used and how detailed it is necessary to specify the molecular species as a component, "each constituent component" is appropriately determined. do it. For example, only molecular species having a certain abundance (abundance ratio) or more in a multi-component mixture may be regarded as "constituent components". It is not always necessary to identify the molecular structures of a huge number of molecular species such as petroleum, and molecular species that exist only in trace amounts may be ignored if necessary. For example, when a polycyclic aromatic resin component (PA) is targeted as a "multicomponent mixture", the presence of paraffinic compounds and olefinic compounds as components constituting PA may be ignored.

(4) "fraction"
The term “fraction” is a concept that includes all of them, such as mass fraction, volume fraction, mole fraction, etc., as long as they indicate the proportion of existence. When calculating the average Hansen Solubility Index value for the entire liquid phase, the volume fraction is preferably used, and is calculated as a weighted average value weighted by the volume fraction of each component in the liquid phase.

(5) "Specify molecular structure", "molecule"
"Specifying the molecular structure" includes any action as long as it is an action of specifying some kind of information about the structure of the molecule with respect to the "molecule" in the above-mentioned "ingredient". Depending on the purpose and necessity, the degree and display method may be selected as appropriate. Structural information about a portion of a molecule may be incorporated as well as the act of specifying the structure of the entire molecule. For example, only the structure of the core portion may be specified, and the molecular formulas of the side chain portions and the cross-linked portions may be left as they are without specifying the structures.
In this specification, the molecular structure is preferably specified by "JACD" described later. A molecule whose structure is specified by "JACD" is a concept that includes all isomers due to differences in the binding positions of attributes described later. As used herein, the term "molecule" may be understood as a concept that includes all isomers.

(6) "Specify the abundance ratio of each component"
"Specify the proportion of each component present" includes any action as long as it is an action of specifying the proportion in which each component constituting a mixture exists. In addition, it does not mean that the abundance ratio of all component species that make up the mixture must be specified, but includes components that are present in amounts that are difficult to detect with analytical techniques and components that do not need to be specified. It does not mean that "the existence ratio of each component has been specified" for the first time after specifying the abundance ratio of all the components. Such trace components and the like may be collectively treated as "other components". Furthermore, these may be excluded from the scope of "each component constituting the mixture" and not included in the denominator for calculating the abundance ratio of other components.

(7) "All"
As used herein, "all" does not necessarily mean "100% of all." For example, where reference is made to "all peaks" in a mass spectrum, not only does it literally mean "100% of all peaks", but it also refers, for example, to molecules that are not necessarily required for the purposes of the discussion in that context. It may be understood that peaks or peaks that are difficult to discriminate are appropriately excluded and other peaks are indicated.

(8) "Peak"
The horizontal axis of peaks obtained in mass spectrometry is m/z for the molecular ions or pseudo-molecular ions of each component constituting the multicomponent mixture. Since the numerical value indicated by m/z is a numerical value corresponding to the mass of a molecular ion or pseudo-molecular ion, it generally represents the molecular weight of the molecule assigned to that peak. In this specification, this "m/z peak for molecular ions or pseudo-molecular ions obtained in mass spectrometry" may be referred to as "peak obtained in mass spectrometry" or simply "peak". Also, the height of the peak indicates the relative abundance of molecules belonging to that peak.

(9) "molecular formula"
A "molecular formula" is a formula that indicates only the types and numbers of elements that constitute a molecule, and indicates that the structure is not specified. Since the types and numbers of elements constituting the molecule are known, information such as the molecular weight and the DBE value described later can be obtained.
Mass spectrometry by the Fourier transform ion cyclotron resonance method mainly used in the present invention (hereinafter also referred to as "FT-ICR-mass spectrometry", the spectrum obtained by FT-ICR-mass spectrometry is referred to as "FT-ICR-mass spectrometry spectrum ), the value of m/z can be determined to four decimal places. Therefore, the molecular formula of the molecule attributed to the peak can be determined by performing accurate mass number matching in consideration of the presence of atomic isotopes. Since the molecular formula only expresses the types and numbers of elements constituting the molecule, a molecule corresponding to the determined molecular formula may have a plurality of isomers. That is, multiple isomers having the same molecular formula can be attributed to one peak.
However, due to the characteristics of FT-ICR-mass spectrometry, even if the molecular formula is the same, for example, hydrogen ions are added to the molecular ions, resulting in a different mass from the original molecular ions. may appear as a peak of Therefore, even if the peaks appear as different peaks in the measurement, those having the same kind and number of elements constituting the molecular formula may be regarded as "the same molecular formula". In the phrase "molecules corresponding to the molecular formula", "the molecular formula" may be understood to mean "the same molecular formula". In addition, the term "certain peak" may be considered as a concept that collectively captures all peaks of various m/z that represent "the same molecular formula" in the above sense.

(10) "core", "single core", "double core"
The “core” is one type of “attribute” described in the section “JACD” described later, and specifically includes an aromatic ring or a naphthenic ring itself, or a direct bond between the aromatic ring and the naphthenic ring instead of a bridge. or a hetero ring directly bonded to an aromatic ring or naphthenic ring instead of being bridged. Since the bridges or side chains are separate attributes from the core, "core" means without any bridges or side chains.
On the other hand, "single core" is a concept that indicates a molecule having only one core. Since it is a concept that refers to molecules, it also includes those in which side chains are bound to the core. A molecule in which two or more of the above cores are crosslinked is called a "multicore". Since "multicore" also means a molecule, it also includes those in which side chains are attached to the core. A molecule in which two cores are crosslinked is called a “double core”.
For example, the naphthalene molecule shown below is a "single core" because it consists of one aromatic ring, and is not a double core consisting of two benzene rings.

(11) "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)
(Wherein, 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 unsaturation in the molecule, especially the presence of double bonds and rings.

(12) "JACD""Juxtaposed Attributes for Chemical-structure Description)"
"JACD" is a new display method for molecular structure, which displays the molecular structure by the type of attribute and the number of attributes. It does not indicate where the attribute is bound to other attributes.
In the above description, the term “attribute” is a concept that refers to chemical structural parts (parts) that constitute a molecule. In aromatic compounds, it specifically refers to the aforementioned "core", "bridges" and "side chains".
According to this display system, for each of the vast number of molecules that make up petroleum, their structure can be specified to the necessary and sufficient extent.
A molecule represented by the following chemical formula will be described as an example.

The JACD of this compound is shown in Table 1 below.

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

(13) "Physical property value"
"Physical property value" is a value obtained based on the molecular structure and its abundance ratio specified by the above method, and if it expresses the physical or chemical properties, properties, and characteristics of the substance , are included in "physical property values" regardless of their names. As used herein, the term "physical property" includes, but is not limited to, melting point, Hansen solubility index, Gibbs free energy of formation, ionization potential, polarizability, dielectric constant, vapor pressure, liquid density , API degree, gas viscosity, liquid viscosity, surface tension, boiling point, critical temperature, critical pressure, critical volume, heat of formation, heat capacity, dipole moment, enthalpy, entropy, etc.

(14) “Oil”
As used herein, the term “petroleum” includes crude oil, fractions obtained by distilling crude oil, and fractions obtained by subjecting the fractions to secondary processing such as reforming and cracking. A generic concept that includes Alternatively, it may refer to a fraction obtained by further fractionating a fraction obtained by distilling crude oil into components such as saturated hydrocarbons and aromatic hydrocarbons.
(15) “Equipment related to petroleum”
As used herein, the term “petroleum-related equipment” includes all equipment related to petroleum processing, including distillation equipment, extraction equipment, reforming equipment, hydrogenation reaction equipment, desulfurization equipment, and other equipment involving chemical reactions. "Equipment related to petroleum" is also generally referred to as "oil refining equipment".

<Identification of the molecular structure of each component of the multicomponent mixture>
Next, each step for identifying the molecular structure of each component of the multi-component mixture in this embodiment will be described with reference to the flow chart of FIG.
(1) Step 1 (mass spectrometry) (S1 in FIG. 1)
Step 1 is a step of performing mass spectrometry on the multi-component mixture, identifying the molecular formula of the molecule assigned to each of the obtained peaks, and further identifying the abundance ratio of the molecule. That is, it is a step of performing mass spectrometry on a multi-component mixture, identifying the molecular formulas of molecules attributed to each peak for all the peaks obtained thereby, and further identifying the proportion of molecules corresponding to the molecular formulas. .

Mass spectrometry preferably uses an ultra-high resolution mass spectrometer. In particular, FT-ICR-mass spectrometers are used to perform highly accurate measurements in a known manner, namely by soft ionizing the sample to form molecular or pseudo-molecular ions.

(2) Step 2 (collision-induced dissociation) (S2 in FIG. 1)
Step 2 is the step of performing collision-induced dissociation on the multi-component mixture. “Collision Induced Dissociation (hereinafter also referred to as “CID”)” refers to an operation of ionizing a molecule and colliding it with an inert gas such as argon to cut crosslinks and side chains. Generally, it is preferable to apply collision energy so that cross-links and side chains in each component constituting the multi-component mixture are broken. Fragment ions for each core are generated by cleaving the bridges and side chains. This core may have, as a side chain, an aliphatic group having about 0 to 4 carbon atoms that could not be cleaved by collision-induced dissociation.
When FT-ICR-mass spectrometry is performed on a multicomponent mixture, the m/z of the resulting peaks can be used to determine the molecular formulas of the molecules that make up the multicomponent mixture. is not obtained. Therefore, if collision-induced dissociation is further performed to cut the crosslinks and side chains in each molecule that constitutes the multicomponent mixture, the types of cores present in the entire multicomponent mixture can be known.
The conditions for collision-induced dissociation are preferably collision energy capable of effectively severing crosslinks and side chains in the molecule, for example, 10 to 50 kcal/mol, more preferably 20 to 40 kcal/mol. 40 kcal/mol corresponds to 32 eV when the molecular weight is 700.

(3) Step 3 (identification of structure and existence ratio of each core) (S3 in FIG. 1)
Step 3 is a step of performing mass spectrometry, preferably FT-ICR-mass spectrometry, on each fragment ion generated by collision-induced dissociation in step 2 to identify the structure and abundance ratio of cores that make up each fragment ion. be.

(a) First, a method for specifying the structure of the core that constitutes each fragment ion will be described.
Specifically, it is a method of collating the information about the cores obtained in step 2 with the information about the cores described in the core structure list prepared in advance to specify the structure of each core.
Details are as follows.
i. Acquisition of information on the core after collision-induced dissociation In FT-ICR-mass spectrometry of each fragment ion after collision-induced dissociation, even if the core part is the same, the number of carbon atoms in the side chain is about 0 to 4. Fragment ions having an aliphatic group of have different masses depending on the type of side chain, so they appear as separate peaks. Therefore, for a core having an aliphatic group having 0 to 4 carbon atoms as a side chain, the mass of each of these is calculated in advance, and the different peaks that appear are compared and collated in various ways, and the mass of the core itself can be assigned.
Using this method, in step 2, for each of the peaks obtained after collision-induced dissociation, the core attributed to that peak is how many masses and how many heteroatoms such as O, N or S atoms are present. , and information on how many aromatic rings are present can be obtained from the DBE value.

ii. Specification of core structure after collision-induced dissociation As a method of specifying the core structure after collision-induced dissociation, various cores that can be assumed to constitute each component molecule of a multi-component mixture are listed as models in advance. Create a "core structure list", compare the information such as the molecular weight of the core, the type and number of heteroatoms stored in the list with the information on the core obtained above, and There is a method of selecting a core model that is considered to be the most appropriate from the above and assigning the selected core as the relevant core.
By this method, cores are assigned to all peaks obtained in FT-ICR-mass spectrometry after collision-induced dissociation, making it possible to know their structures.

iii. Core structure list The types of cores to be stored in the core structure list are not particularly limited and may be of any type. It is directly related to validity.
It is preferable to prepare a "core structure list" in advance according to the content of the multi-component mixture itself, which is a sample. For example, when the multi-component mixture is petroleum, a "core structure list for specifying the molecular structure of petroleum" may be prepared in advance based on the knowledge about petroleum so far and used.
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 preferable to store an appropriate number of cores in consideration of various conditions such as which position and in what form the naphthene ring is bonded.
For example, the size of the aromatic ring is up to 6 rings, and the heteroatom is assumed to be N, O, S, and the number of types of heterocycles is about 10, etc., considering convenience in calculation. Just make a list.

iv. Selection from Core Structure List There may be multiple structures in the core structure list that have the same molecular weight, DBE value, and type and number of heteroatoms, but different structural formulas. In this case, it suffices to appropriately determine a rule as to which one of the plurality is to be selected as the first priority. For example, as the priority, the following 1 to 3 can be mentioned.
1. Preference is given to those consisting only of aromatic rings.
2. Prioritize those with many unsaturated bonds.
3. Prioritize those with fewer rings.

(b) Next, a method for specifying the existence ratio of each core will be described.
As described above, from the height of each peak obtained after collision-induced dissociation in step 2, the m/z, that is, the existence ratio of cores having that mass can be obtained.
The structure of each core after collision-induced dissociation obtained in this step 3 will be used later in step 5, and the existence ratio of each core after collision-induced dissociation will be used later in step 4. It will be.

(4) Step 4 (Estimation of existence state and existence ratio of cores for each class) (S4 in FIG. 1)
Molecules belonging to each of the peaks in step 1 are divided into “classes” based on “types and numbers of heteroatoms (including zero) and DBE values”, and all molecules belonging to each “class” , is the step of estimating the existence mode and the existence ratio thereof.
In other words, the molecules belonging to all the peaks in step 1 are classified into “classes” based on “type and number of heteroatoms (including zero) and DBE value” in each molecular formula specified in step 1. It is a step of dividing and estimating the mode of existence and the proportion of all molecules belonging to each of the "classes".

Step 4 will be described in detail below.
(a) Since the molecular formulas are specified for all peaks in step 1, the type and number of heteroatoms in the molecular formula and the DBE value are known. Therefore, in this step, each of the molecules assigned to all the peaks is grouped by "type, number, and DBE value of heteroatom" based on the "type, number, and DBE value of heteroatom." into each "class".
"Type and number of heteroatoms" is specifically "the number of heteroatoms for each type of heteroatom". The heteroatom is preferably a nitrogen atom, a sulfur atom and an oxygen atom, so the "type and number of heteroatoms" preferably means "the number of nitrogen atoms, sulfur atoms and oxygen atoms". can also Therefore, with regard to heteroatoms, "the number of nitrogen atoms, the number of sulfur atoms, and the number of oxygen atoms are all the same" belong to the same "class".

(b) Next, in each class bounded by "type and number of heteroatoms and DBE value" described in (a), each molecule belonging to that class is estimated to be single-core or multi-core. . In addition, it is estimated in what ratio the single-core and multi-core are present.
In performing these estimations, it is preferable to make some assumptions for practical calculation convenience.
Here, "multi-core" can be combined in various ways depending on what kind of cores are crosslinked and bonded. However, the sum of the DBE values of a plurality of cores forming a multi-core and the sum of numbers corresponding to the types of heteroatoms are the same for all those belonging to the class.

(c) As described above, the molecules assigned to each of the peaks obtained by FT-ICR-mass spectrometry were grouped into classes having the same type and number of heteroatoms and the same DBE value. Molecules belonging to that class are single-core or multi-core. A preferred method for estimating what kind of cores these single cores or multicores are composed of will be described below.

When a molecule belonging to the class is a single core, it is a single core having the type and number of heteroatoms and DBE value corresponding to the class. When the molecule belonging to the class is multi-core, the sum of the number of heteroatoms of the same type present in the multiple cores constituting the multi-core and the sum of the DBE values of these multiple cores is This is the combination of cores consistent with the type and number of heteroatoms and the DBE value of the class. Since the sum of the numbers corresponding to the types of heteroatoms and the sum of the DBE values of the multiple cores should correspond to the types, the number, and the DBE values of the heteroatoms of the class, the combination of multiple cores that constitute the multi-core is usually not limited to one, but exists in several ways.

(d) Next, it is estimated that "in what ratio are single-core molecules and multi-core molecules that belong to the class exist?"
Preferably, first, it is assumed that the existence ratio of a multi-core is the product of the respective existence ratios of the multiple cores that make up the multi-core, and this is taken as an estimated value.

(5) Step 5 (Determination of Core Structure, Side Chains and Crosslinks) (S5 in FIG. 1)
Step 5 is a step of determining the structure of the core that constitutes each molecule whose existence mode was estimated in step 4, and further determining and allocating side chains and crosslinks.

(a) "Determining the structure of the core forming each molecule" for "each molecule whose existence mode was estimated in step 4" is performed by the following operations i to v.
i. If the mode of existence is estimated to be multi-core in step 4, separate (release) each core that constitutes it.

ii. The same "type and number of heteroatoms and DBE value" for all cores whose existence mode was estimated to be single core in step 4 and cores generated by canceling multicore as in i above to each "class". Incidentally, the "class" here is a concept related to cores obtained by releasing the original single core and multicore, and is different from the "class" related to molecules described in Step 4.

iii. Allocate specific structures for all cores existing in the "classes" of "types and numbers of heteroatoms and DBE values" enclosed in ii above.

(b) The side chains and crosslinks are further determined by the operations i to iii below.
i. By the above, the structure of the core part of a single core or multi-core could be specified, but if only the existence of the core part was assumed, the FT-ICR-mass spectrometry of the target sample could not be obtained. The m/z of the obtained peak does not match the indicated mass. That is, the sum of the masses due to the carbon, hydrogen and heteroatoms involved in the core part differs from the m/z masses of the peaks obtained by FT-ICR-mass spectrometry.
Therefore, it is considered that the difference in mass is derived from the presence of the side chains bonded to the core and the crosslinks that bond the cores together. Assign it to the core as side chains and bridges.
For example, suppose that a certain double core obtained by cross-linking core 1 and core 2 is assigned to a certain peak of m/z=n by the above procedure. At this time,
The difference in mass (d) = n - (mass of core 1 + mass of core 2)
is due to the presence of side chains and crosslinks.

ii. In the above i., the number of carbon atoms and the number of hydrogen atoms assigned to the side chains and crosslinks are determined, but the structure of the side chains and crosslinks has not yet been determined. Therefore, in estimating what kind of structure side chains and crosslinks correspond, considering the existence probability of the combination of side chains and crosslinks, for example, the following rules are determined, and according to them Just guess. As a rule, conditions such as the upper limit of the number of carbon atoms constituting side chains and crosslinks and the number of side chains may be determined in advance.
iii. In i above, if there are no side chains or bridges corresponding to the difference in mass, a structure in which core 1 and core 2 are simply bonded may be applied.
(c) “Assigning to cores” the side chains and crosslinks determined above does not include determining to which position of which core the side chains and crosslinks are bound.

(d) In this way, in step 5, for each single core or double core whose existence state was estimated in step 4, the structure of the cores constituting them can be determined, and the side chains and crosslinks can be determined. can.

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

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

In carrying out fractionation, there is no particular limitation on the criteria used as boundaries between fractions or the method for fractionation. Specifically, it is preferable to carry out by the following methods.
In this method, a multi-component mixture is subjected to a highly accurate type-based separation pretreatment to fractionate into multiple components. Particularly in the case of heavy oils, it is preferable to carry out such a fractionation. The method of "separation pretreatment by type" is not particularly limited, and it may be separated into several components according to arbitrary standards, but column chromatography fractionation method, Soxhlet extraction method and 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 chromatography fractionation method, such as the method described in JP-A-2011-133363. The number of components to be fractionated may be appropriately selected according to the purpose.

Specifically, the method includes the following first to third steps.
(First step)
Heavy oil is separated into n-paraffin-soluble maltene and other insolubles.
(Second step)
The maltene content separated in the above (first step) was subjected to column chromatography to obtain saturated content (Sa), single-ring aromatic content (1A), two-ring aromatic content (2A), three-ring or more aromatic content ( 3A+), polar resin fraction (Po) and polycyclic aromatic resin (PA) fractions.
(Third step)
More preferably, the 3- or more-ring aromatic fraction (3A+) obtained in the second step is further subjected to Peri-type 4-ring aromatics and Cata-type 4-ring aromatics using preparative liquid chromatography. and optionally 5 or more ring aromatics (5A+).

<Method for Determining Composition Model of Multi-Component Mixture by Computer>
Next, a method for determining a composition model of a multi-component mixture using a computer will be described.
This includes step A of fractionating the multi-component mixture into two or more arbitrary parts, and for each fraction fractionated in step A, the molecules of each component constituting each fraction by the method described above. A step B of specifying the structure and abundance ratio, and a step C of integrating 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 comprising:
As described above, the "multicomponent mixture A" is regarded as a mixture of fractions as many as the number of fractions, such as fraction I, fraction II, etc. obtained by fractionating it, and each For the fraction, the molecular structure and abundance ratio of each component constituting the fraction are specified by the method described above. After that, if all the components of all fractions are integrated according to the mixing ratio of each of fraction I, fraction II, etc. in "multicomponent mixture A", that is, according to the fractional yield, "multicomponent mixture With regard to the entire composition model of A", it is possible to specify what kind of components and in what proportions it is composed.

<Step of obtaining melting point and Hansen solubility index value of each component of multi-component mixture>
Next, the step of obtaining the melting point and Hansen Solubility Index value of the multi-component mixture in this embodiment will be described.
(6) Step 6 (acquisition of melting point and Hansen Solubility Index values) (S6 in FIG. 1)
Obtaining the melting point and Hansen solubility index value (hereinafter also referred to as "HSP value") of each component from the molecular structure of each component of the multicomponent mixture identified using JACD in steps (1) to (5) .
These physical property values are preferably specified for the molecular structure of each component of the multi-component mixture specified as described above using the complete petroleum molecule database (Comcat).

Comcat is a "JACD-physical property value database" in which JACD and each physical property value are linked. The number of registered molecules in this database is about 25 million, and it can be used in model system analysis assuming that all components contained in petroleum are composed of molecules contained in Comcat.

The physical property values registered in the database are melting point, Hansen Solubility Index, boiling point, critical humidity, critical pressure, critical volume, vapor pressure, liquid density, gas viscosity, liquid viscosity, surface tension, dipole moment, polarizability. , ionization potential, heat of formation, enthalpy, entropy, free energy, heat capacity, etc., about 200 physical properties.

These physical property values are usually calculated using the atomic group contribution method or the molecular orbital method. The atomic group contribution method is used to determine the physical property values of a substance by specifying the chemical structure of the substance, and based on the unique parameter values of the various existing atomic groups, that is, the “groups” of the substance. 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 a premise that the "group" of the substance is specified first, and the structure is specified based on that.
In the present invention, as described above, for each component that constitutes the multi-component mixture, the various atomic groups present are specified, so that the component can be calculated. Furthermore, since the abundance ratio of each component is also specified, if this abundance ratio is considered, it is possible to appropriately estimate the physical property values of the entire multi-component mixture from the physical property values of each component.

<Step of estimating properties of multicomponent mixture using multicomponent aggregation model>
Next, the step of estimating properties of a multi-component mixture by a multi-component aggregation model using the melting point and Hansen solubility index value of each component obtained above will be described.

Before describing the embodiments of the present invention, a multi-component aggregation model (MCAM) on which the present invention is based will be described in steps (7) to (16) below.

(7) Step 7 (separation into liquid phase component and non-liquid phase component) (S7 in FIG. 1)
In steps (1) to (6) above, the fraction, melting point and Hansen Solubility Index value of each component are obtained, and the desired temperature T is set.
Among the components constituting the multicomponent mixture, those having a melting point lower than the desired temperature T are classified as liquid phase components, and those having a melting point equal to or higher than the desired temperature T are classified as non-liquid phase components. Here, the desired temperature T is as defined above.

(8) Step 8 (calculation of the average HSP value of the entire liquid phase) (S8 in FIG. 1)
For the HSP value of each component classified as a liquid phase component in step (7), a weighted average value weighted by the volume fraction of each component in the liquid phase is calculated as the average HSP value of the entire liquid phase. The volume fraction can be calculated by obtaining in advance various information on physical properties such as density and molecular weight for each component.

(9) Step 9 (Calculation of HSP value difference between entire liquid phase and each non-liquid phase component) (S9 in FIG. 1)
A difference (Δδ) between the average HSP value of the entire liquid phase calculated in step (8) and the HSP value of each component in the non-liquid phase component is calculated.

(10) Step 10 (Update Classification of Each Component Based on Δδ) (S10 in FIG. 1)
Each component in the non-liquid phase component is reclassified as a liquid phase component or a non-liquid phase component based on the difference (Δδ) calculated in step (9), and each component reclassified as a liquid phase component is classified as a non-liquid phase component. Incorporating from the phase component to the liquid phase component updates the liquid phase component and the non-liquid phase component.
The update in this reclassification may be performed for each component in the non-liquid phase component one by one, or may be performed for each of a plurality of components.

(11) Step 11 (calculation of average HSP value of entire liquid phase after update) (S11 in FIG. 1)
For the HSP value of each component in the liquid phase component after updating in step (10), the weighted average value weighted by the volume fraction of each component in the liquid phase after updating is calculated as the average HSP of the entire liquid phase after updating Calculate as a value.

(12) Step 12 (repeat steps 9-11) (S12 in FIG. 1)
Steps (9)-(11) are repeated until the final stage when no non-liquid phase components are reclassified as liquid phase components in step (10).

(13) Step 13 (calculation of degree of aggregation of non-liquid phase components) (S13 in FIG. 1)
Calculate the degree of agglomeration D of the non-liquid phase components after updating at the final stage at the desired temperature.

(14) Step 14 (classification of non-liquid phase components based on degree of aggregation) (S14 in FIG. 1)
Each component in the non-liquid phase component after updating in the final stage is classified into a condensed phase component and a solid phase component based on the cohesion degree D.

(15) Step 15 (calculation of average aggregation degree of aggregation phase components) (S15 in FIG. 1)
An average degree of condensation D of the cohesive phase components classified in step 14 is calculated.

(16) Step 16 (output properties of multicomponent mixture) (S16 in FIG. 1)
The information obtained from the above steps outputs the properties of the multi-component mixture.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.

<Identification of the molecular structure of each component of the multicomponent mixture>
The method for estimating properties of a multi-component mixture by computer according to the present invention will be described by applying each step shown in the flow chart of FIG. 1 to an assumed model. As a "multi-component mixture", a polycyclic aromatic resin component (PA) is used as a model.
(1) Step 1 (mass spectrometry) (S1 in FIG. 1)
In step 1, the molecular formula of each component constituting the multi-component mixture and the proportion of molecules corresponding to the molecular formula are specified. For example, looking at the spectrum chart obtained by FT-ICR-mass spectrometry in FIG. 4, many peaks appear near the mass (m/z) of 303.2. For each of its peaks, the molecular formula of the assigned molecule is precisely specified.
In addition, since the ratio of the height of a certain peak to the sum of the heights of all peaks represents the abundance of molecules belonging to that peak, the abundance of molecules corresponding to the molecular formula of each component can be identified from that height. do.

(2) Step 2 (collision-induced dissociation (CID)) (S2 in FIG. 1)
In step 2, collision-induced dissociation is performed on the multi-component mixture.
As shown in FIG. 2, a parent ion having 40 carbon atoms and DBE=17 is dissociated into two fragment ions by collision-induced dissociation to cut side chains and crosslinks. The sum of the DBE value "17" of the molecule (parent ion) before CID and the DBE values "10" and "7" of the two molecules (fragment ions) after CID is equal.
By CID, as shown in FIG. 2, most of the molecules with cross-links are cleaved of cross-links and side chains, and under appropriate conditions, consist of a core and side chains of no more than 4 carbon atoms.

(3) Step 3 (identification of structure and existence ratio of each core) (S3 in FIG. 1)
In step 3, each fragment ion generated by CID in step 2 is subjected to FT-ICR-mass spectrometry to identify the structure and abundance of cores that constitute each fragment ion. That is, for each fragment ion after CID, the structure and abundance ratio of the core attributed to the peak obtained by FT-ICR-mass spectrometry are specified.
A method for specifying the structure and abundance ratio of each core will be described with reference to the schematic diagram of FIG. Here, the m/z value of the FT-ICR-mass spectrum after CID and the accurate mass of the core stored in the core structure list are compared and collated to assign the core to each peak. At that time, the cores contained in the "core structure list" are collated, selected and assigned so that the molecular weight, molecular formula, and DBE value obtained from the m/z of the peak match.
Here, for every peak of the FT-ICR-mass spectrum after CID, the assigned core structure, molecular weight, type and number of heteroatoms and DBE values will be specified.
For the cores assigned to each peak, the abundance ratio can be known from the relative heights of the assigned peaks.

(4) Step 4 (Estimation of existence state and existence ratio of cores for each class) (S4 in FIG. 1)
In step 4, the molecules belonging to each of the peaks in step 1 are divided into "classes" based on "type and number of heteroatoms (including zero) and DBE value", and belong to each of the "classes" For all molecules, the existence mode and abundance ratio are estimated.
(a) First, summarize the peaks obtained by FT-ICR-mass spectrometry of the target multi-component mixture by “class” of “type and number of heteroatoms and DBE value” as follows are expressed as peaks.
Description will be made with reference to FIG. The upper part of FIG. 6 shows “the peak itself obtained by FT-ICR-mass spectrometry”. For the peak obtained by FT-ICR-mass spectrometry, the molecular formula of the molecule assigned to that peak, the type and number of heteroatoms, and the DBE value are known. Therefore, first, as shown in the middle of FIG. 6, among all the molecules assigned to all peaks, the molecules with no heteroatom in the molecular formula are first bundled as a “group of zero heteroatoms”, and then Then, all the molecules that have been found to exist in the "zero heteroatom group" are divided by "DBE value" and peaked. Next, as shown in the lower part, molecules having one nitrogen atom in the molecular formula are bundled as "group of N atom = 1", and then exist in the "group of N atom = 1" All the molecules that have become are divided by "DBE value" and peaked. In this way, for all "groups of types and numbers of heteroatoms", the corresponding molecules are bundled and peaks are obtained for all molecules existing in the groups by "DBE value".

In the above, the "group with zero heteroatoms" was described, but in the case of molecules that have only one nitrogen atom as a heteroatom in the molecular formula, they are bundled as "N1 molecular group", and all belonging there are divided into "classes" for each "DBE value". For example, a "class" that collects DBE values of 22 is divided into "N1 molecule group DBE value 22 classes". In addition, in the case of a molecule having one nitrogen atom and one sulfur atom as heteroatoms in its molecular formula, they are grouped together as a separate group called "N1S1 molecular group". Further, molecules having the same "kind and number of heteroatoms and DBE value" belong to the "same class" even if the molecular formulas are different due to the different numbers of carbon atoms and hydrogen atoms.
As described above, it is possible to represent a collection of molecules bounded by a unit called "class" as a peak.

(b) Next, for each "DBE value peak" in each group of "type and number of heteroatoms", what kind of core the peak is composed of is estimated.
In this case, it is preferable to make some assumptions for practical calculation convenience. An example of "DBE value=22" will be described below.
When the DBE value is 22, the cores to be considered include a single core with a DBE value of 22 and a multi-core composed of a plurality of cores with a total DBE value of 22.
Here, assumption (1) is set as follows.
Assumption (1): "All multi-cores shall consist of two cores, i.e. only double-cores."
Therefore, when DBE=22, a single core consists of one core with DBE=22, and a double core consists of two assumed cores (here, "core A and core B ) are as shown in Table 2 below.

なお、ＣＩＤ後のＦＴ－ＩＣＲ－質量分析の結果を見ると、ＤＢＥ値が１～５のコアは存在しておらず、ＤＢＥ値＝１～５のコアは考慮する必要がないと言える。よって、ダブルコアの組合せとしては、「１６－６、１５－７、１４－８、１３－９、１２－１０、１１－１１」となる。
即ち、「ＤＢＥ値＝２２」のピークは、以下の表３のようなコアから構成されていることになる。

Looking at the results of FT-ICR-mass spectrometry after CID, there are no cores with DBE values of 1 to 5, and it can be said that there is no need to consider cores with DBE values of 1 to 5. Therefore, the combination of double cores is "16-6, 15-7, 14-8, 13-9, 12-10, 11-11".
That is, the peak of "DBE value=22" is composed of cores as shown in Table 3 below.

(c) Next, the ratio of each core is estimated.
In this estimation, the following assumptions (2) and (3) are set and determined for i. double-core (multi-core) case and ii. single-core case.

i. For double-core, set assumption (2) as follows.
Assumption (2): Among double cores made up of a combination of two cores with a DBE value sum of 22, for example, “the existence ratio of a double core made up of a core with a DBE value of 12 and a core with a DBE value of 10 is is the product of the existence ratio of cores with a DBE value of 12 and the existence ratio of cores with a DBE value of 10", and this value is an estimated value. FIG. 7 schematically shows the existence ratio of double cores based on assumption (2).
Here, the existence ratio of cores with a DBE value of 12 after CID is the ratio of the peak height of the DBE value of 12 to the sum of the peak heights of all DBE values.
That is, the existence ratio of a peak with a DBE value of 12 is (sum of peak heights for molecules having a DBE value of 12 after CID)/(sum of heights of all peaks after CID).
The existence ratio of those with a DBE value of 10 is the same.
For a double core composed of another combination of two cores with a DBE value sum of 22, for example, a core with a DBE value of 14 and a core with a DBE value of 8, the existence ratio of the double core can be similarly estimated. .

ii. For the single core case, set assumption (3) as follows.
Assumption (3): It is assumed that the existence ratio of a single core with a DBE value of 22 is "the value obtained by dividing the existence ratio of the peak with a DBE value of 22 after CID by the DBE value of 22". Then, this divided value is used as an estimated value. FIG. 8 schematically shows the existence ratio of single cores based on assumption (3).
As described above, the existing ratios of single cores and various double cores with a DBE value of 22 can be estimated.

In the above, the case of "the DBE value in the heteroatom = zero group = 22" was described, but in the target multicomponent mixture, when the heteroatom = zero, the DBE value = 13 to 32 is present ( FIG. 6 middle row), similarly, for each DBE value, the existence mode of the core attributed thereto is estimated.
Furthermore, when N=1, when N=2, . In such a case, the number of possible types of cores in multi-cores is enormous, depending on where the heteroatom exists. Thus, for example, an assumption may be made that "heteroatoms are not present in side chains and bridges, but only in the core." In addition, in the case of a group in which a large number of heteroatoms are present, for example, "a group in which one nitrogen atom and one sulfur atom are present (N1S1 group)", "one of the two cores bonded by a bridge, nitrogen There is one atom, and there is one sulfur atom on the other side."
As described above, it is possible to estimate what kind of single-core or multi-core each molecule consists of.

(d) Next, it is estimated that "in what ratio are single-core molecules and multi-core molecules that belong to the class exist?" Preferably, first, it is assumed that the existence ratio of a multi-core is the product of the respective existence ratios of the multiple cores that make up the multi-core, and this is taken as an estimated value.

In the above example, among double cores obtained from a combination of two cores with a DBE value sum of 22, for example, the existence ratio of a double core consisting of a core with a DBE value of 12 and a core with a DBE value of 10 is "DBE after CID The product of the existence ratio of cores with a DBE value of 12 and the existence ratio of cores with a DBE value of 10 is assumed to be the estimated value.

Here, since the existence ratio of cores with a DBE value of 12 after CID is the ratio of the height of the peak with a DBE value of 12 after CID to the sum of the heights of all peaks after CID, steps 2 and 3 already It can be calculated using known values. In addition, the existence ratio of objects with a DBE value of 10 can also be known in the same manner. Further, for double cores having a sum of DBE values of 22, for example, a core with a DBE value of 13 and a core with a DBE value of 9, the existence ratio of the double cores can be similarly estimated.
In this way, even if the type and number of heteroatoms and the DBE value are reclassified for each "class" composed of molecules, it is possible to estimate the existence ratio of various multi-cores belonging to the class. can.

Further, as the next assumption, the existence ratio of a single core with a DBE value of 22 is the value obtained by dividing the existence ratio of the peak with a DBE value of 22 after CID by the DBE value of "22". is preferable.
Assuming the above, it is possible to estimate the existing ratios of single cores and various multi-cores with a DBE value of 22. FIG.

(5) Step 5 (determination of core structure, side chains, crosslinks) (S5 in FIG. 1)
In step 5, for each molecule whose existence mode was estimated in step 4, the structure of the core constituting them is determined, and side chains and crosslinks are determined and assigned.
(a) First, for each molecule whose mode of existence was estimated in step 4, the structure of the core constituting them is determined and allocated. Specifically, it is as follows.

(A-1) "Preparation"
All the cores are grouped into respective "classes" for the same "kind and number of heteroatoms and DBE value" by the following procedures i to v.
i. If the state of existence is estimated to be double cores in step 4, this is temporarily canceled, and each constituent core is considered separately. In other words, all cores including all cores generated by canceling the double core as well as the original single core are treated as independent ones.
For example, in the above example, as shown in FIG. will be divided into cores of (In the previous example, looking at the results of FT-ICR-mass spectrometry after CID, there were no cores with DBE values of 1 to 5, so cores with DBE values of 1 to 5 need not be considered. can be excluded.)
For the other DBE values, the double core is canceled and the cores are divided.
As shown in FIG. 10, for example, when the DBE value is 20, the cores are divided into cores with DBE values of 6, 7, 8, 9, 10, 11, 12, 13, 14, and 20, similar to the case of 22. It will be.

ii. All cores generated from the original single core and the released double core are then grouped by DBE value. For example, for those with a DBE value of 10, all those with a DBE value of 10 generated by release are collected regardless of the original double core. DBE values of 12, etc. are all collected in the same way.
At this time, as shown in FIG. 11, each collected as "DBE value=10" differs in abundance depending on its origin. Derived parent (that is, whether the parent has DBE value = 22 and has DBE value = 10, or the parent has DBE value = 20 and has DBE value = 10) proportional.

iii. Furthermore, even if "no heteroatom, DBE value = 10" and "the derived parent has the same DBE value of 22", the mass of the parent peak is different (i.e., side Due to the presence or absence of chains and the difference in the number of chains, there are multiple ones with the same core portion but different masses) are different entities, and the abundance ratio is proportional to the abundance ratio of the parent.

iv. Thus, in the set "no heteroatom, DBE value = 10" there will be a large number of cores that differ depending on which parent they came from.
These many cores are then ordered based on the parent mass from which they are derived, from lowest to highest parent mass, as shown in FIG.

v. Cores containing heteroatoms form separate "classes" according to the type and number of heteroatoms, and proceed in the same manner as above.
Based on the above, all the cores are grouped into respective "classes" for the same "type and number of heteroatoms and DBE value", and arranged according to the order of mass of the parent from which each core belonging to the class is derived. something was created.

(A-2) "Work to allocate structure"
For all the "classes" of "type and number of heteroatoms and DBE values" created above, structures are assigned to all cores existing in the set.
Hereinafter, the class “no heteroatom, DBE value=10” will be described.
i. Assign a structure to each of all cores present in the "class" of "no heteroatoms. DBE value = 10", where the "assigned structure" comes from the core structure identified in step 3. i. be.
That is, in step 3, since the attributed core structure, molecular weight, type and number of heteroatoms and DBE value are specified for all peaks after CID, a certain "type and number of heteroatoms and DBE To the "class" of "value", cores of peaks matching "type and number of heteroatoms and DBE value" among all peaks after CID are assigned. Therefore, since the only requirement is that these values match, there may be multiple corresponding peaks. In that case, multiple structures with different molecular weights will be assigned to one "class".

ii. Apply the cores with "No heteroatoms, DBE value=10" identified in step 3 to all cores present in the set "No heteroatoms, DBE value=10". In step 3, as cores having "no heteroatom. DBE value = 10", only the following two types of core X and core Y with different molecular weights are identified from the core structure list, and their abundance ratio is the peak after CID Assume that the core X is 30% and the core Y is 70% based on the height ratio.

「ヘテロ原子なし。ＤＢＥ値＝１０」の組に存在しているコアは、構造としては、この２種のいずれかが割り付けられることになる。

Cores that exist in the set of "no heteroatom, DBE value=10" are assigned either of these two types of structures.

iii. How to assign core X and core Y to each core existing in the set "no heteroatom, DBE value=10" is performed as follows.
In the above "preparation", based on the mass of the originating parent, those arranged in order from small to large were prepared. In this arrangement, as shown in FIG. A line is drawn at 30:70, and the core X is assigned to the side with the smaller mass, and the core Y is assigned to the side with the larger mass.
As described above, the structure is assigned to all cores existing in the set of "no heteroatom, DBE value=10".

(A-3) "Work to return to multi-core structure"
As described above, all the cores to which the structures and existence ratios have been allocated are returned to the original double cores before cancellation, whose existence mode was estimated in step 4 .
At this time, for example, in the case of a double core consisting of a core 1 with a DBE value of 12 and a core 2 with a DBE value of 10, a certain structure α is specified in the core 1 with a DBE value of 12 in (A-2) above. , and since a certain structure β is specified for core 2 with a DBE value of 10, the structure of the core portion of this double core is specified. In addition, since the existence ratio of the core of structure α and the core of structure β are also specified in step 3, from the assumption (2) of step 4, the ratio of existence of the double core with DBE value = 22 is the core of structure α and the product of the abundance ratio of cores in structure β.

(b) "Work to determine side chains and crosslinks and assign them to core species"
Subsequently, the side chains and crosslinks are determined and assigned to the core in steps i and ii below.
Here, "assigning to a core" does not mean to include determining to which position of which core a side chain or crosslink is attached.
i. In the above, the structure and abundance ratio of the core portion of the single core or double core could be specified, but the side chains that bind to the core and the crosslinks that bind the cores to each other are still unknown. Not decided.
By the way, if only the core portion is assumed, its molecular weight does not match the m/z value of the peak obtained by FT-ICR-mass spectrometry. That is, even the sum of the masses due to the carbon, hydrogen and heteroatoms involved in forming the core results in a difference in m/z values in the peaks obtained by FT-ICR-mass spectrometry.
Therefore, it is considered that the difference is derived from the existence of the side chains that bind to the core and the crosslinks that bind the cores together. Allocate to the core as chains and crosslinks.
For example, suppose that the structure of the core portion consisting of "core 1 - core 2" is assigned to a certain m/z=n peak by the above procedure. At this time,
The difference (d) = n - (mass of core 1 + mass of core 2)
is due to the presence of side chains and crosslinks.

ii. In i above, the number of carbons and hydrogen atoms to be assigned to the side chains and crosslinks is determined, but the structure of the side chains and crosslinks has not yet been determined.
Therefore, in estimating what kind of structure side chains and crosslinks correspond, considering the existence probability of the combination of side chains and crosslinks, for example, the following rules are determined, and according to them Just guess.
Rule 1: Mass difference (d) up to a certain value X shall be derived only from cross-linking without side chains.
Rule 2: If the mass difference (d) exceeds a certain value X, it is assigned to side chains after allocating crosslinks according to Rule 1. A rule is also set for the maximum number of carbon atoms per side chain, and assignment is made accordingly.

(c) In this way, the core structure is determined, and the side chains and crosslinks are determined for all the core species whose existence mode was estimated in step 4.

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

Next, an example in which a multi-component mixture is subjected to type-specific separation pretreatment will be described.
I. Fractionation by Type As a sample, vacuum residue (VR) obtained by vacuum distillation of atmospheric residue was used. Vacuum residuum (VR) is the equivalent of heavy oil. Saturated content (Sa), 1-ring aromatic content (1A), 2-ring aromatic content (2A) obtained by performing a pretreatment method (first and second steps) on vacuum residue (VR), Fractions of three or more ring aromatics (3A+), polar resins (Po) and polycyclic aromatic resins (PA), and fractions of asphaltenes (As) separated from maltene in the first step , the respective yields were obtained.

Incidentally, the first and second steps of the pretreatment method were carried out by the following method.
<First step: Separation of maltene>
7 g of a sample was weighed into a conical flask with a capacity of 500 ml, 220 ml of n-heptane was added, and the mixture was boiled under reflux for 1 hour using an n-heptane insoluble content tester with an air condenser attached.
After boiling under reflux, the mixture was allowed to stand for cooling, and the asphaltenes were separated using filter paper to obtain a fraction containing maltene.

<Second Step: Separation of Maltene by Column Chromatography>
The maltene fraction obtained in the first step was separated by column chromatography under the following conditions.
(1) Column conditions for column chromatography Column: 15 mm × 600 mm (gel-filled part, made of glass)
Gel: 40g silica gel + 50g alumina gel (after activation)
Silica gel: Chromato Gel Grade 923AR manufactured by Fuji Silysia
Alumina gel: MP BiomebicaLs, MP Alumina, Activated, Neutral, Super I
Activation conditions: silica gel 250° C.×20 h, alumina gel 400° C.×20 h, 0.2 kg/cm ² (N ₂ gas) pressurization Sample amount: 1.5 g (maltene)

(2) Separation method The following solvents were sequentially charged into the column, and the eluted solution was collected.
(i) 200 ml of n-heptane is added, and the eluted sample solution up to 250 ml is cut as a saturated portion (Fr. Sa).
(ii) Add 250 ml of a mixed solvent of 95% n-heptane and 5% toluene, and cut up to 200 ml of the eluted sample solution 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) 250 ml of toluene is added, and 300 ml of the eluted sample solution is cut and taken as aromatics with 3 or more rings (Fr.3A+).
(v) Add 250 ml of ethanol, cut 230 ml of the eluted sample solution, and use it as a polar resin (Fr. Po).
(vi) Add 100 milliliters of chloroform. Subsequently, (vii) 100 ml of ethanol is added, and (vi) and (vii) are repeated.
All of (vi) and (vii) are collected as one fraction and used as a polycyclic aromatic resin (Fr. PA).

The results were as follows.
Saturated content (Sa) 10%, 1-ring aromatic content (1A) 11%, 2-ring aromatic content (2A) 8%, 3- or more ring aromatic content (3A+) 35%, polar resin content (Po) 9 %, polyaromatic resin content (PA) 16%, and asphaltenes content (As) 11%.

II. Identification of Molecular Structure (1) Step 1
Perform mass spectrometry on the sample by FT-ICR-mass spectrometer, identify the molecular formula of the molecule assigned to each peak for all the peaks obtained by the mass spectrometry, and furthermore, the abundance ratio of all molecules corresponding to the peak identified.

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.
- Used sample: Polycyclic aromatic resin (PA) obtained by the above type fractionation.
・Sample preparation method: Dissolve several tens of milligrams of a sample in chloroform, drop about 1 µL onto a MALDI (matrix-assisted laser desorption/ionization) plate, and use it as a measurement sample after the solvent evaporates.
Ionization method: Laser desorption ionization method (LDI method) (number of shots: 2000, oscillation frequency: 1000 Hz, power: 23%).
As a result of the measurement, the mass spectrum shown in FIG. 14 was obtained.

(b) The specified molecular formulas and abundance ratios (in mole fractions) for each peak in the mass spectrum are shown in Table 4 below.
The number of peaks is 3030. Only some of them (peak numbers 11 to 3022 are omitted) are shown below. In the table, the peak numbers are given in ascending order of m/z value.

(2) Step 2
By subjecting the sample to collision-induced dissociation (CID), the crosslinks and side chains of each component constituting the sample were cut.
Details are as follows.
Samples were prepared and ionized in the same manner as in step 1 above.
As a collision induction condition, the collision energy was set to 30 eV.
The mass spectrum obtained after CID is shown in FIG.

(3) Step 3
FT-ICR-mass spectrometry was performed on each fragment ion generated by CID in step 2 to identify the structure and abundance ratio of cores constituting each fragment ion.
For each peak in the mass spectrum after CID, the molecular weight, molecular formula, and DBE value of the core stored in the core structure list prepared in advance were collated to identify each core structure and abundance ratio.
A portion of the core structure list used is shown below.

このステップ３は、コア構造リストの情報をコンピュータに組み込んでおくことにより、コンピュータを用いて実行された。

This step 3 was performed using a computer by incorporating the information of the core structure list into the computer.

(4) Step 4
Molecules assigned to all peaks in step 1 are divided into "classes" based on "type and number of heteroatoms and DBE value" in each specified molecular formula, and all molecules belonging to each "class" , the existence mode and existence ratio were estimated.
Since step 4 is a process processed by a computer, it is not possible to extract the result in the middle.

(5) Step 5
For each molecule whose existence mode was estimated in step 4, the structure of the core constituting them was determined, and the side chains and crosslinks were determined and assigned.
Since step 5 is a process processed by a computer, it is not possible to extract the result in the middle.

(6) Step 6
<Identification of the molecular structure for the mass spectrum of the sample>
Although the number of peaks obtained in step 1 is 3030, a plurality of molecules having the same molecular formula belong to one peak, that is, a peak showing a certain molecular formula. In this example, 38,964 JACD-expressed molecules with different structures were identified for the above 3030 types of molecular formulas.
Some of the results (peak numbers 4 to 3028 omitted) are shown in Table 6 below. How to read the table is as follows.
(a) Peak numbers are assigned so as to correspond to the peak numbers in Table 4 shown in Step 1.
Peak number 1 has a molecular formula of “C ₂₁ H ₁₉ N”, which indicates that molecules with different structures displayed by the four types of JACD were assigned to this molecular formula.
(b) Of the four types of molecules with the molecular formula "C ₂₁ H ₁₉ N", for example, "molecular species number 1" will be described. The structure of this molecule is indicated by JACD using alphanumeric characters.

(c) In the table above, in order to convert the JACD representation using alphanumeric characters into the structures of the core, crosslinks and side chains, a code table may be prepared in which the alphanumeric information is converted into structural information. For example, the table is as follows.

(d) Using this table, the structure of _the molecule of "molecular species number 1" of the molecular formula " _C21H19N " is as follows.
Since i.core 1 is "002007", the structure is as follows.

ii. コア２は「００４０００」であるため、以下の構造である。

ii. Core 2 is "004000", so the structure is:

iii. 架橋1は「０ＢＣ００３」であるため、以下の構造である。

iii. Bridge 1 is "0BC003", so the structure is:

iv. 側鎖はすべて「００００００」であるため、存在しないという意味である。
v. このようにして、分子式「Ｃ_２１Ｈ_１９Ｎ」の「分子種番号１」の分子について、ＪＡＣＤにより構造を表示し、特定することができた。
（カ）同様にして、すべての分子について、ＪＡＣＤにより構造を表示し、特定することができた。

iv. The side chains are all "000000", meaning they are absent.
v. In this way, the structure of the molecule with the molecular formula "C ₂₁ H ₁₉ N" and "molecular species number 1" could be identified by JACD.
(f) Similarly, the structures of all molecules could be displayed and specified by JACD.

III. Integration of data for each fraction
(1) Saturated content (Sa), 1-ring aromatic content (1A), 2-ring aromatic content (2A), 3- or more ring aromatic content (3A+), polar resin content (Po) and asphaltenes content (As) Also, the molecular structure was specified in the same manner as for the polycyclic aromatic resin, except that the following was changed.
(A) Atmospheric pressure photoionization method (APPI method) (sample flow rate 200 μL/h, The ion accumulation time was 0.2 sec., and the number of times of accumulation was 100.).
(a) Asphaltene content was ionized by the laser desorption ionization method (LDI method) (number of shots: 5000, oscillation frequency: 1000 Hz, power: 17%).

(2) Integration of all fractions: saturates (Sa), single-ring aromatics (1A), double-ring aromatics (2A), aromatics with three or more rings (3A+), polar resins ( Po), polycyclic aromatic resin (PA), and asphaltene content (As), the molecular structure and abundance ratio of all components for all fractions are determined according to the respective yields (abundance ratios) obtained above. Integrated.

(3) From the above, it was possible to specify the molecular structure and abundance ratio of all the molecules constituting the vacuum residue (VR) for the sample vacuum residue (VR).

<Acquisition of Melting Point and Hansen Solubility Index HSP Value (δt) of Each Component of Multicomponent Mixture>
In estimating the properties of the model heavy oil, first, based on the JACD of each component specified above, the fraction, melting point and HSP value (δt) of each component constituting the model heavy oil are obtained from Comcat.

In this embodiment, a model heavy oil containing 11 types of components (molecular species O-01 to O-11) shown below is used as a multi-component mixture, and the properties of this model heavy oil (dissolution, aggregation and An example of estimating the precipitation properties) by computer will be described.

Table 8 shows the molecular composition (fraction) of the model heavy oil, and the estimated melting point and HSP value (δt) of each molecule.

The melting point and HSP value (δt) of each molecule shown in Table 8 above may be obtained from a database, or may be calculated using a computer by the atomic group contribution method.
An example of calculating the HSP value (δt) and the melting point by the atomic group contribution method will be described below.

i. How to obtain the HSP value (1) In the case of "O-01" molecule Use the numerical values of Fd value, Fp value, Eh value and Vc value shown for the groups forming the molecule in the literature of Krevelen & Hoftyzer. can be calculated by the Krevelen & Hoftyzer method.

As the atomic group contribution method, for example, D.I. W. van Krevelen, K.; ｔｅ Ｎｉｊｅｎｈｕｉｓ著「Ｐｒｏｐｅｒｔｉｅｓ ｏｆ Ｐｏｌｙｍｅｒｓ（４ｅｄ．２００９）」に記載のＫｒｅｖｅｌｅｎ ＆ Ｈｏｆｔｙｚｅｒの方法や、Ｅｍｍａｎｕｅｌ Ｓｔｅｆａｎｉｓ， Ｃｏｓｔａｓ Ｐａｎａｙｉｏｔｏｕ著「Ｐｒｅｄｉｃｔｉｏｎ ｏｆ Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒｓ ｗｉｔｈ ａ Ｎｅｗ Ｇｒｏｕｐ－Ｃｏｎｔｒｉｂｕｔｉｏｎ Ｍｅｔｈｏｄ」に記載のＳｔｅｆａｎｉｓ ＆ Ｐａｎａｙｉｏｔｏｕのmethod etc. can be used.

For these, it is also possible to use a program that estimates from the molecular structure. Such programs include, for example, HSPiP (https://www.hansen-solubility.Com/).
Furthermore, it is also possible to use values obtained by appropriately modifying the values obtained by these various methods as a reference.

HSP values are reported in the literature (Hansen, CM, Hansen solubility parameters: a user's handbook. 2nd ed.; CRC: Boca Raton; London, 2007) for more than 1200 substances. Therefore, the literature value can also be used.

A summary of the Krevelen & Hoftyzer method is as follows. First, it is widely known that the HSP value (δt) of a substance can be obtained by the following formula.

FIG. 16 shows a schematic diagram of HSP values. _The HSP value is _a solubility index that indicates how much a certain substance dissolves in a certain solvent _. It is represented by a vector.

Next, δd, δp, and δh are obtained by the following equations according to the Krevelen & Hoftyzer atomic group contribution method.

In the formula, the Fd value ((MJ/m ³ ) ^1/2 mol ⁻¹ ) is the molar attraction constant of each group (atomic group) resulting from the dispersion force, and the Fp value ((MJ/m ³ ) ^1/2 mol ^-1 ) is the molar attraction constant of each group (atomic group) caused by the force between dipoles, and the Eh value (J mol ^-1 ) is the is the hydrogen bond energy.

式中、Ｖｃは各基（原子団）のモル体積である。
Ｄ．Ｗ．ｖａｎ Ｋｒｅｖｅｌｅｎ，Ｋ．ｔｅ Ｎｉｊｅｎｈｕｉｓ著「Ｐｒｏｐｅｒｔｉｅｓ ｏｆ Ｐｏｌｙｍｅｒｓ（４ｅｄ．２００９）」の文献によれば、多くの基について、Ｆｄ値， Ｆｐ値， Ｅｈ値， Ｖｃ値が示されているため、当該文献にて値が記載されている基については、その値を用いればよい。（Ｄ．Ｗ．ｖａｎ Ｋｒｅｖｅｌｅｎ ， Ｋ．ｔｅ Ｎｉｊｅｎｈｕｉｓ著「Ｐｒｏｐｅｒｔｉｅｓ ｏｆ Ｐｏｌｙｍｅｒｓ（４ｅｄ．２００９）」１９５～１９７ページ及び２１５ページ）。値が記載されていない基については、構造的に近似する他の基の情報を用いて推定した値を用いるなどを行えばよい。
上記のようにして、Ｋｒｅｖｅｌｅｎ ＆ Ｈｏｆｔｙｚｅｒ法によりＨＳＰ値（δｔ）を算出することができる。 Also, V is the molar volume (cm ³ ·mol ⁻¹ ) and can be obtained by the following formula (3) proposed by Rheineck and Lin.

In the formula, Vc is the molar volume of each group (atomic group).
D. W. van Krevelen, K.; According to the document "Properties of Polymers (4ed.2009)" by Te Nijenhuis, Fd value, Fp value, Eh value, and Vc value are shown for many groups, so the values are described in the document. For the groups that have (DW van Krevelen, K. te Nijenhuis, "Properties of Polymers (4 ed. 2009)" pages 195-197 and 215). For groups for which values are not described, values estimated using information on other structurally similar groups may be used.
As described above, the HSP value (δt) can be calculated by the Krevelen & Hoftyzer method.

In the case of the "O-01" molecule, the groups consist of 2 "CH ₃ -" and 28 "-CH ₂ -". According to the aforementioned Krevelen & Hoftyzer document, "CH ₃ -" has an Fd value of 420 and a Vc value of 33.5, and "-CH ₂ -" has an Fd value of 270 and a Vc value of 16. .1, these values are used, and from the above formulas (3) and (2), δd of "O-01" is {(420 × 2) + (270 × 28)} / { (33.5×2)+(16.1×28)}=16.22. Similarly, δp and δh can be calculated as HSP value (δt)=16.22.

Calculation is performed in the same manner for the molecules “O-02” to “O-11”. Regarding the groups forming the molecule, the values described in the Fd value, Fp value, Eh value and Vc value may be used for the groups described in the literature of Krevelen & Hoftyzer. For groups not described, values estimated using information on other structurally similar groups may be used.

ii. Method for Determining Melting Point Estimation of the melting point is one of the atomic group contribution methods, and is described in "Joback, K.G., Reid, R.C., Chem. Eng. Comm., 57, 233 (1987)." The described Joback method may be used. That is, a molecular species is decomposed into “groups” forming its molecular structure, and the melting point of the molecular species is calculated from the inherent parameter values of each group. When using "average molecular structure", melting point of said "fraction based on specific physical or chemical properties" using atomic group contribution method based on said structure Calculate

(7) Step 7 (separation into liquid phase component and non-liquid phase component) (S7 in FIG. 1)
Next, among the components constituting the multi-component mixture, those having a melting point lower than a desired temperature are classified as liquid phase components, and those having a melting point equal to or higher than the desired temperature are classified as non-liquid phase components.
For example, in the case of the model heavy oil, if the liquid temperature is 250 ° C., "O-01" to "O-03", "O-09" and "O-10" having melting points lower than this temperature ' molecules are classified as liquid phase components, while 'O-04' through 'O-08' and 'O-11' molecules with melting points above this temperature are classified as non-liquid phase components.

(8) Step 8 (calculation of the average HSP value of the entire liquid phase) (S8 in FIG. 1)
Next, for the HSP value of each component classified as a liquid phase component, a weighted average value weighted by the volume fraction of each component in the liquid phase is calculated as the average HSP value of the entire liquid phase.

(9) Step 9 (Calculation of HSP value difference between entire liquid phase and each non-liquid phase component) (S9 in FIG. 1)
Next, the difference between the average HSP value of the entire liquid phase and the HSP value of each component in the non-liquid phase component is calculated.

(10) Step 10 (Update Classification of Each Component Based on Δδ) (S10 in FIG. 1)
Next, each component in the non-liquid phase component is reclassified as a liquid phase component or a non-liquid phase component based on the difference (Δδ), and each component reclassified as a liquid phase component is changed from the non-liquid phase component to the liquid phase component. Incorporate into the phase component to update the liquid phase component and the non-liquid phase component.
For example, in the case of the model heavy oil, RED represented by RED=Δδ/ _R0 was judged to be a liquid phase component when RED<0.3. Here, R ₀ is a constant for each component in the non-liquid phase component, and RED was calculated with R ₀ =5 for the model heavy oil.
The update in this reclassification may be performed one by one for each component in the non-liquid phase component, or may be performed for each of a plurality of components.

(11) Step 11 (calculation of average HSP value of entire liquid phase after update) (S11 in FIG. 1)
Next, for the HSP value of each component in the liquid phase components after updating, the weighted average value weighted by the volume fraction of each component in the liquid phase after updating is calculated as the average HSP value of the entire liquid phase after updating. do.

(12) Step 12 (repeat steps 9-11) (S12 in FIG. 1)
Steps 9-11 are then repeated until the final stage where no non-liquid phase components are reclassified as liquid phase components in step 10 .
In this way, the liquid phase component after updating in the final stage is taken as the liquid phase component of the model heavy oil at that temperature, and the average HSP value after updating in the final stage is taken as the model heavy oil at that temperature. is determined as the average HSP value for the entire liquid phase at . In addition, the sum of the fractions of each classified component in the liquid phase component after updating in the final stage is calculated as the liquid phase fraction.

(13) Step 13 (calculation of degree of aggregation of non-liquid phase components) (S13 in FIG. 1)
Subsequently, the aggregation degree D of the non-liquid phase component after updating in the final stage at the desired temperature is calculated.

(14) Step 14 (classification of non-liquid phase components based on degree of aggregation) (S14 in FIG. 1)
Next, each component in the non-liquid phase component after updating in the final stage is classified into a condensed phase component and a solid phase component based on the aggregation degree D.

Furthermore, based on these results, parameters representing various properties of the model heavy oil are calculated. For example, the aggregated phase fraction is calculated as the aggregated phase fraction, and the solid phase fraction is calculated as the solid phase fraction. Furthermore, a value obtained by dividing the sum of the degree of aggregation of each component classified as the aggregated phase component by the number of the components is calculated as the average degree of aggregation of the entire aggregated phase.

By the above method, for this model heavy oil, first calculate and estimate the amount and composition of the liquid phase, aggregated phase and solid phase without solvent, the degree of aggregation D of each molecule in the aggregated phase, and the average degree of aggregation of the aggregated phase. did. The experiment was carried out from -50°C to 350°C at 100°C intervals.
Table 9 shows what phase each molecule exists at each temperature. It also indicates the molecular composition of each phase.

Furthermore, FIG. 17 shows the amount of each phase and the average degree of aggregation of the aggregated phase at each temperature. In FIG. 17, "Liquid" means "liquid phase", "Aggregate" means "aggregate phase", and "Solid" means "solid phase". "Phase wt ratio" means "mass fraction of each phase". Furthermore, "Averaged Dagg" means "average degree of cohesion". "Temperature" means "temperature". The same applies to other drawings in this specification.

As shown in Table 9 and FIG. 17, in the absence of a solvent, up to 150° C. all are solid phases, above 250° C. all are condensed phases or liquid phases, and at 350° C. the ratio of liquid phases increases. The average degree of cohesion of the cohesive phase is 1.53 and 1.25 at 250°C and 300°C, respectively.

<Processing method for multi-component mixture>
Next, an embodiment of the method for treating a multi-component mixture of the present invention will be described.
In processing, as described above, the properties of the model heavy oil are estimated as the original multi-component mixture, and when the model heavy oil is mixed with a solvent or the temperature is changed, a new model Properties of heavy oil are predicted by the above method. Then, under the same conditions as predicted, the solvent is mixed with the model heavy oil in that fraction, or the solution is treated by changing the temperature of the model heavy oil to the temperature at the time of prediction.

Accordingly, in the present invention, the amount and composition of each of the liquid phase, the aggregated phase, and the solid phase in the solution calculated or estimated by the above method, the degree of aggregation of each component in the aggregated phase, and the average degree of aggregation of the aggregated phase Based on the above, the solution can be treated by dissolving all or part of the aggregated and solid phases, or by taking measures to inhibit aggregation or precipitation of components.

I. Aggregation Relaxation Treatment First, as a treatment example, a treatment for dissolving an aggregated phase and a solid phase in a solution, or for suppressing aggregation or precipitation of components will be described. Once the amount and composition of each of the liquid, aggregated and solid phases in the solution and the degree of aggregation of each component in the aggregated phase and the average degree of aggregation of the aggregated phase are known, all or part of the aggregated phase and solid phase can be It is possible to obtain guidance on what measures should be taken in order to dissolve or suppress aggregation or precipitation of components.

Here, the amount and composition of the liquid phase, the aggregated phase and the solid phase, and the average aggregation degree of the aggregated phase were calculated and estimated when the model heavy oil was made into a 30% by mass toluene solution. Table 10 below shows what phase each molecule exists at each temperature. It also indicates the molecular composition of each phase.

Furthermore, FIG. 18 shows the amount of each phase and the average cohesion degree of the aggregated phase at each temperature.

As shown in Table 10 and FIG. 18, in the toluene solution, even at -50° C., the solid phase is only 10%, and 90% is the condensed phase dispersed in the solvent. At 50°C, 100% of the liquid phase becomes the condensed phase. It can be seen that the average degree of cohesion of the cohesive phase decreases with increasing temperature from 1.81 at -50°C to 1.27 at 350°C.

Furthermore, for the toluene solution of the model heavy oil, in order to dissolve the aggregated phase and solid phase, based on the O-11 molecule with the largest HSP value, the type of solvent to be added so that the O-11 molecule is dissolved and quantity will be determined. Specifically, the solvent is changed from toluene to an equal mass ratio of toluene and bromobenzene (HSP value 20.4 (δd = 21.0, δp17 = 2.5, δh = 2.0, δt = 20.4)) By changing to a mixed solvent, all aggregated phases and solid phases can be dissolved at a liquid temperature of 350°C.

Furthermore, FIG. 19 shows the amount of each phase and the average degree of aggregation of the aggregated phase at each temperature.

In this way, depending on the precipitation amount and precipitation properties of the flocculated phase and solid phase in the model heavy oil,
There are various measures that can be taken, but specific examples include adding the same solvent as the current one, adding a new solvent (solvent) of a different kind, raising the temperature of the solution, and the like. In particular, with regard to the addition of a solvent (solvent), any It can be determined what amount of solvent (solvent) having an HSP value should be added.

II. Precipitation Promotion Treatment Next, as a treatment example, a treatment for promoting precipitation in a solution will be described.
If the amount and composition of each of the liquid, aggregated and solid phases in the solution and the degree of aggregation of each component in the aggregated phase and the average degree of aggregation of the aggregated phase are known, the estimated liquid phase and aggregated phase in the solution and the amount and composition of each of the solid phases and the degree of cohesion of each component in the cohesive phase and the average cohesion of the cohesive phase. can be obtained.

In this way, there are various measures that can be taken depending on the properties of the liquid phase in the solution, but specifically, for example, adding a new solvent (solvent) or lowering the temperature of the solution be done. In particular, with regard to the addition of a solvent (solvent), any It can be determined what amount of solvent (solvent) having an HSP value should be added.

Thus, it is possible to calculate and estimate the amount and composition of the liquid phase, the aggregated phase and the solid phase in the solution, and to calculate the degree of aggregation of each component in the aggregated phase and the average degree of aggregation of the aggregated phase. Therefore, if measures such as appropriately selecting the solvent type, adding a new solvent, or changing the temperature of the solution are taken, all or part of the aggregated phase and solid phase in the solution can be It is possible to dissolve or inhibit aggregation or precipitation of components, or to precipitate one or more components.

In the above embodiment, an example in which properties of a model heavy oil are estimated as a multi-component mixture has been described, but in the present invention, the multi-component mixture is not limited to heavy oil.

<Apparatus for estimating properties of multi-component mixture>
Next, with reference to FIG. 20, an embodiment of the multi-component mixture property estimation device of the present invention will be described. FIG. 20 is a functional block diagram of the multi-component mixture property estimation device of the embodiment. By causing a computer to execute the program of the present invention, the computer functions as an apparatus for estimating properties of multicomponent mixtures.
Note that FIG. 20 omits illustration of an interface for inputting and outputting information.

This device comprises an arithmetic unit 1 and a storage unit 2 . The arithmetic unit 1 may be configured with one CPU, or may be configured with a plurality of arithmetic units connected to each other via a communication line. The storage unit 2 may be built in the arithmetic device 1, may be an external device, or may be a storage device connected via a communication line.

This arithmetic device 1 has a component information acquisition section 10 , an initial classification section 20 , a liquid phase arithmetic section 30 and a non-liquid phase arithmetic section 40 .

I. Component Information Acquisition Unit The component information acquisition unit 10 acquires the fraction, melting point, and HSP value of each component that constitutes the target multi-component mixture. Information on these components may be obtained from the storage unit 2 in which information on the multi-component mixture is stored as a database.

If the information on these components is not stored in the database, the component information calculator 11 should estimate the necessary parameters for each component.

As an example of a method of estimating the melting point and HSP value of components constituting a multi-component mixture, a method based on information on molecular composition (molecular structure) can be cited.

(1) In this method, first, it is necessary to obtain information on the molecular composition (molecular structure) of each molecular species constituting the sample solution. Here, the molecular species constituting the solution does not strictly refer to all molecular species present in the solution, but molecules having a certain amount (proportion of existence) or more in the solution You can think of it as referring to seeds. It is desirable to target as many molecular species present in the solution as possible, but molecular species present in only trace amounts may be ignored. A sample solution may be subjected to a component analysis in advance, and the amount (abundance ratio) of each molecular species present may be used as a criterion for selecting the target molecular species.

Alternatively, as described above, the "component" is a "mass of a solution based on a certain physical or chemical property", in other words, "a fraction based on a certain physical or chemical property" When used in the sense of "fraction", this "method based on information on molecular composition (molecular structure)" can be applied as follows.
That is, by measuring NMR, elemental analysis, mass spectrum, etc. for each of "fractions fractionated based on a certain physical or chemical property", using a known method , the "average molecular structure" of that fraction can be obtained. Using the "average molecular structure" thus obtained, this method can be applied.

(2) Next, based on the obtained JACD of each molecular species, the melting point data of each molecular species is obtained from Comcat. The processing is performed by a computer.

(3) Also, based on the JACD of each molecular species, obtain HSP value data of each molecular species from Comcat. The processing is performed by a computer.

(II. Initial classifier)
The initial classification unit 20 classifies components having a melting point lower than a desired temperature among the components constituting the multi-component mixture as liquid phase components, and classifies components having a melting point equal to or higher than the desired temperature as non-liquid phase components. do. That is, at or above some arbitrary temperature above the melting point of the solvent, the amount and composition of the "liquid phase" at that temperature is determined. Components with melting points below that temperature are components that are in the liquid phase. The amount and components of the "liquid phase" at this time are determined.

(III. Liquid phase calculation unit)
The liquid phase calculation unit 30 includes an average HSP calculation unit 31, a Δδ (HSP value difference) calculation unit 32, a reclassification unit 33, and a liquid phase component information calculation unit 34 in order to estimate properties of the liquid phase. I have.

The average HSP calculator 31 calculates the average HSP value of the entire liquid phase. Here, the average HSP value of the entire liquid phase is calculated as a weighted average value obtained by weighting the HSP value of each component in the liquid phase by the fraction, preferably volume fraction, of each component in the liquid phase. be.

The HSP value difference (Δδ) calculator 32 calculates the difference (Δδ) between the average HSP value of the entire liquid phase and the HSP value of each component in the non-liquid phase components.

The reclassification unit 33 reclassifies each component in the non-liquid phase component into a liquid phase component and a non-liquid phase component based on the difference (Δδ), and classifies each component reclassified as a liquid phase component into a non-liquid phase component. The liquid phase component and the non-liquid phase component are updated by incorporating from the phase component to the liquid phase component.
The reclassification unit 33 recalculates the HSP value of the entire liquid phase by adding the dissolved component, if any, to the liquid phase.

The average HSP calculator 31 calculates the updated average HSP value of the entire liquid phase. Here, the average HSP value of the entire liquid phase after updating is the weighted average value obtained by weighting the HSP value of each component in the liquid phase component after updating by the fraction of each component in the liquid phase, preferably the volume fraction. It is calculated.

Then, the update of the average HSP value, the liquid phase component and the non-liquid phase component (coagulated phase, solid phase) is repeated until the final stage where there are no non-liquid phase components to be reclassified as liquid phase components.

Furthermore, the liquid phase information calculation unit 34 calculates the sum of the fractions of the liquid phase components after the update at the final stage as the liquid phase fraction.

(IV. Non-liquid phase calculation unit)
The non-liquid phase calculation unit 40 has an aggregation degree calculation unit 41, an aggregation phase/solid phase classification unit 42, an aggregation phase information calculation unit 43, and a solid phase information calculation unit 44 in order to estimate properties of the non-liquid phase. . The non-liquid phase calculation unit 40 determines the properties of the non-liquid phase, for example, the amount and components of the aggregated phase, the degree of aggregation of each of the aggregated components, the average degree of aggregation of the aggregated phase, and the amount and composition of the solid phase. .

The aggregation degree calculation unit 41 calculates the aggregation degree of each component in the non-liquid phase component after updating at the final stage at the desired temperature by combining the average HSP value of the entire liquid phase and the HSP value of each component in the non-liquid phase component. and the concentration C of each component in the non-liquid phase components after updating in the final stage. Specifically, they are classified as follows.

For each component in the non-liquid phase component that did not finally dissolve in the liquid phase, the degree of aggregation is determined based on its HSP value and the HSP value of the entire liquid phase. The aggregation degree D of each aggregated component is calculated by the function formula (A) with the variables of the HSP value of the liquid phase, the HSP value of the aggregated component, the concentration of the aggregated component, and the temperature of the field. can do.

^D ( _{p ,q)=M AS (K0+K1p+K2q+K3p2} ⁺ _{K4pq + K5q2 +} ^K6p3 ₊ ^K7p2q _{+ K8pq2} ⁺ _K9q3 ⁾ ₍ A)

where p is
When the desired temperature T is T≦150° C.,
p=(L ₀ (T−25)+L ₁ )RED _g ,
When the desired temperature T is 150° C.<T≦200° C.,
p=(L ₀ (150−25)+L ₁ )RED _g ,
When the desired temperature T is 200° C.<T,
p=(L ₀ (T−25)+L ₂ )RED _g
is represented by

RED _g is expressed as RED _g = RED when RED≧0.3, RED _g =0.3 when RED<0.3, RED is expressed as RED=Δδ/R ₀ , Δδ is the difference between the average HSP value of the entire liquid phase and the HSP value of each component in the non-liquid phase components, and R ₀ is a constant for each component in the non-liquid phase components.

L ₀ , L ₁ and L ₂ are empirically derived coefficients and have the following constant values.
L ₀ =−0.0031262,
_L1 = 1.07815,
_L2 = 1.15631

q is expressed as q=log C, where C is the concentration of the aggregated component in the non-liquid phase component.

_MAS is a constant determined according to the type of component, and is as follows when, for example, the aggregate phase component and solid phase component of the multi-component mixture are asphaltenes. Canadian oil sand asphaltenes (CaAs): 1.319, Middle East asphaltenes 1 (ArAs1): 1.000, Middle East asphaltenes 2 (ArAs2): 1.136.

K ₀ -K ₉ are empirically derived coefficients and have the following constant values.
K ₀ =−1.26929,
_K1 = 9.42231,
_K2 = 0.363439,
_K3 = -11.1925,
_K4 = 0.093622,
_K5 = -0.15436,
_K6 = 5.337433,
_K7 = -0.20868,
_K8 = 0.077223,
_K9 = 0.019492
is.

From the above, when a certain component is aggregated in a certain solution at a certain temperature, the value of the aggregation degree D of the aggregated component can be calculated.
It should be noted that the numerical values of L ₀ , L _{1 ,} L _{2 ,} M _AS and K ₀ to K ₉ shown in the above can take various numerical values depending on the object, and are limited to the above numerical values. is not.

The aggregation phase/solid phase classification unit 42 classifies, among the non-liquid phase components after the update in the final stage, those components whose degree of aggregation is less than a predetermined threshold as aggregated phase components, and the components whose degree of aggregation is equal to or greater than the predetermined threshold. are classified as solid phase components. That is, the component whose degree of aggregation is at the level of aggregation is defined as the aggregated phase component, and the component whose degree of aggregation is at the level of precipitation is defined as the solid phase component. Here, "at the aggregation level" conceptually means that the size of the aggregated particles is several hundred nm or less and dispersed in the liquid, and "at the precipitation level" means that the aggregated particles It is considered that the size is submicron or more and cannot be dispersed in the liquid and is precipitated. When the degree of agglomeration D≧5, it can be generally determined that the component species precipitates, but this threshold can vary depending on the component species.

The aggregated phase information calculation unit 43 calculates the total amount of each component classified as the aggregated phase component (fraction with respect to the entire solution) as the aggregated phase fraction. Furthermore, the aggregated phase information calculation unit 43 calculates a value obtained by dividing the sum of the degrees of aggregation of each component classified as the aggregated phase component by the number of the components as the average degree of aggregation of the entire aggregated phase.

The solid phase information calculator 44 calculates the total amount of each component classified as a solid phase component (fraction with respect to the entire solution) as a solid phase fraction.

<Program for estimating properties of multi-component mixtures>
In the present invention, a series of processes of estimating the molecular structure using JACD, linking the estimated molecular structure information and physical property values, and estimating the properties of the multicomponent mixture using the aggregation model can be performed by hardware or software. , or a combination of these. When executing processing by software, install the program recording the processing sequence in the memory within the computer built into the dedicated hardware and execute it, or install the program in a general-purpose computer capable of executing various processing. can be executed by

For example, the program can be recorded in advance on a hard disk or ROM as a recording medium. Also, the program can be temporarily or permanently stored (recorded) in removable recording media such as flexible disks, CD-ROMs, MO disks, DVDs, magnetic disks, and semiconductor memories.

In addition to installing the program on the computer from the removable recording medium as described above, the program can also be wirelessly transferred from the download site to the computer, or wired to the computer via a network such as a LAN or the Internet. Then, you can receive the program transferred in this way and install it on a recording medium such as a built-in hard disk.

In addition, the various processes described in this specification are not only executed in chronological order according to the description, but may also be executed in parallel or individually according to the processing capacity of the device that executes the processes and as necessary. . Further, in this specification, a system is a logical collective configuration of a plurality of devices, and is not limited to one in which the devices of each configuration are in the same housing.

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. Also, in the above-described embodiment, FT-ICR-mass spectrometry was used as mass spectrometry, but the present invention is not limited to this.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to specify the structure of molecules that constitute petroleum, so that it can be widely applied to analyze various reactions of petroleum at the molecular level. Furthermore, the analysis at the molecular level contributes to dramatically improving the operational stability and operational efficiency of petroleum refining facilities.

Claims (28)

A method for estimating properties of a multi-component mixture by computer, comprising:
(1) performing mass spectrometry on the multi-component mixture, identifying the molecular formula of the molecule assigned to each peak obtained by performing mass spectrometry, and further identifying the abundance ratio of the molecule;
(5) for each molecule whose molecular formula has been specified in step (1), determine the structure of the core that constitutes them, and further determine and assign side chains and crosslinks;
(6) obtaining the melting point and Hansen Solubility Index value of each component from the molecular structure of each component of the multi-component mixture identified in steps (1) and (5);
(7) Among the components constituting the multi-component mixture, classify the component having a melting point lower than the desired temperature as a liquid phase component, and classify the component having a melting point equal to or higher than the desired temperature as a non-liquid phase component. a step;
(8) calculating an average Hansen Solubility Index value for the entire liquid phase as a weighted average value obtained by weighting the Hansen Solubility Index values of each component classified as the liquid phase component by the volume fraction of each component in the liquid phase; ,
(9) calculating the difference between the average Hansen Solubility Index value for the entire liquid phase and the Hansen Solubility Index value for each component in the non-liquid phase components;
(10) Each component in the non-liquid phase component is reclassified as a liquid phase component or a non-liquid phase component based on the difference, and each component reclassified as a liquid phase component is changed from the non-liquid phase component to the liquid phase component. to update the liquid phase component and the non-liquid phase component;
(11) Calculate the average Hansen solubility index value of the entire liquid phase after updating as a weighted average value obtained by weighting the Hansen solubility index value of each component in the liquid phase component after updating by the volume fraction of each component in the liquid phase. a step;
(12) repeating steps (9) to (11) until a final stage where no non-liquid phase components are reclassified as liquid phase components in step (10);
A method for estimating properties of a multi-component mixture, characterized by: 2. The method of claim 1, further comprising the step (2) of subjecting the multi-component mixture to collision-induced dissociation after step (1). After step (2), each fragment ion generated by collision-induced dissociation in step (2) is subjected to mass spectrometry, and a step (3) of specifying the structure and abundance ratio of the core that constitutes each fragment ion. 3. The method of claim 2, further comprising: After the step (3), the molecules belonging to each of the peaks in the step (1) are divided into “classes” based on “type and number of heteroatoms and DBE values”, and each “class” 4. The method according to claim 3, further comprising a step (4) of estimating the abundance and abundance of all molecules belonging to it. In specifying the structure of each core in the step (3), the information about the core after collision-induced dissociation obtained in the step (2) and the information about the core described in the prepared core structure list are combined. 5. A method according to claim 3 or 4, characterized by matching and identifying the structure of each core. 6. The method of claim 5, wherein the core structure list lists the various cores that can be assumed to make up each component of the multi-component mixture. 7. The molecular structure of each component constituting the multi-component mixture is represented by the type of attribute including core, side chain and crosslink, and the number of attributes, according to any one of claims 1 to 6 described method. When the molecule belonging to the class is multi-core, the "state of existence" in the step (4) is the sum of the number of heteroatoms of the same type present in the multiple cores constituting the multi-core and 5. The method of claim 4, wherein the cores are combined such that the sum of the DBE values of these cores matches the type and number of heteroatoms and the DBE value of the class. When the molecule belonging to the class is a multi-core, the "proportion of its presence" in step (4) is defined as the product of the proportion of existence of each of the multiple cores that make up the multi-core. 5. The method of claim 4, wherein: 10. The multi-component mixture according to any one of claims 1 to 9, wherein the multi-component mixture is one fraction obtained by fractionating a certain multi-component mixture into two or more arbitrary parts. the method of. A computer-aided method for determining a compositional model of a multi-component mixture, comprising:
A step of fractionating the multi-component mixture into any two or more portions;
A step B of specifying the molecular structure and abundance ratio of each component constituting each fraction by the method according to any one of claims 1 to 10 for each fraction fractionated in the step A; and step C of integrating the molecular structures and abundance ratios of all components obtained for all fractions according to the mixing ratio of each fraction fractionated in step A. A method of estimating physical properties of a multi-component mixture based on the molecular structure and abundance ratio of each component constituting the multi-component mixture specified by the method according to any one of claims 1 to 10. The liquid phase fraction according to any one of claims 1 to 12, further comprising a step of calculating the sum of the fractions of each component in the liquid phase component after step (12). Method. The degree of agglomeration of each component at the desired temperature in the non-liquid phase component after performing step (12) is calculated by combining the average Hansen Solubility Index value for the entire liquid phase after performing step (12) with the step ( Further having a step of calculating based on the difference between the Hansen solubility index value of each component in the non-liquid phase component after performing 12) and the concentration of each component in the non-liquid phase component after performing step (12) A method according to any one of claims 1 to 13, characterized in that The method according to any one of claims 1 to 14, wherein the aggregation degree (D) of each component in the non-liquid phase component is calculated by the following formula (A).
D( _p , ^q )=M _AS ( _K0 + _K1p +K2q+ _K3p2 ⁺ _K4pq ⁺ _K5q2 ⁺ _K6p3 ⁺ K7p2q _{+ K8pq2} +K ₉ q ³ ) (A)
(In the formula,
p is p = (L ₀ (T − 25) + L ₁ )RED _g when the desired temperature (T) is T≦150° C., and when the desired temperature (T) is 150° C.<T p = (L ₀ (150 - 25) + L ₁ )RED _g when ≤ 200°C and p = (L ₀ (T - 25 ) + L ₂ )RED _g ,
L ₀ , L ₁ and L ₂ are coefficients,
RED _g is expressed as RED _g =RED when RED≧0.3 and RED _g =0.3 when RED<0.3,
RED is expressed as RED=Δδ/ _R0 ,
Δδ is the difference between the average Hansen Solubility Index value for the entire liquid phase and the Hansen Solubility Index value for each component in the non-liquid phase components,
R ₀ is the constant of each component in the non-liquid phase component,
q is represented by q=log C,
C is the concentration of each component in the non-liquid phase component,
M _AS and K ₀ -K ₉ are coefficients. ) Among the components in the non-liquid phase components after the step (12) is performed, the components whose degree of aggregation is less than the predetermined threshold value are classified as aggregated phase components, and the components whose degree of aggregation is the predetermined threshold value or more are solidified. 16. A method according to claim 14 or 15, further comprising classifying as a phase component. calculating the sum of the fractions of each component classified as the aggregated phase component as the aggregated phase fraction;
17. The method of claim 16, further comprising calculating the sum of the fractions of each component classified as the solid phase component as the solid phase fraction. 17. The step of calculating an average cohesion degree of the entire cohesion phase as a value obtained by dividing the sum of the cohesion degrees of each component classified as the cohesion phase component by the number of the components. 17. The method according to 17. A method according to any one of the preceding claims, characterized in that said multi-component mixture is petroleum. A method according to any one of the preceding claims, characterized in that the multi-component mixture contains the desired type of solvent in the desired fraction. Process according to any one of the preceding claims, characterized in that the multi-component mixture is a heavy oil or a mixture of heavy oil and solvent. By the method according to any one of claims 1 to 21, the properties of the original multicomponent mixture are estimated, and further based on the estimation results of the properties,
When the original multi-component mixture is mixed with the desired type of solvent in the desired fraction,
when the temperature of the original multi-component mixture is changed to a desired temperature, or when the original multi-component mixture is mixed with a desired type of solvent in a desired fraction and the temperature of the original multi-component mixture is changed to a desired temperature Predict the properties of the new multi-component mixture when
Based on the prediction, the desired type of solvent is mixed in the desired fraction into the original multicomponent mixture, or the temperature of the original multicomponent mixture is changed to the desired temperature, or the desired mixing a type of solvent in said desired fraction into said raw multi-component mixture and changing the temperature of said raw multi-component mixture to said desired temperature;
A method for treating a multi-component mixture, characterized in that: The desired type of solvent and the desired fraction, and/or the desired temperature are determined so that the predicted properties of the new multicomponent mixture are In claim 22, characterized in that the solvent and fraction and / or temperature are such that all or part of the A method of processing the described multi-component mixture. The desired type of solvent and the desired fraction, and/or the desired temperature are determined so that the predicted properties of the new multicomponent mixture are 24. A method of treating a multi-component mixture according to claim 22 or 23, characterized in that the solvent and fraction and/or the temperature are such that one or more of the components are in a precipitated state. A property estimation device for a multi-component mixture,
a component information acquisition unit that acquires the fraction, melting point, and Hansen solubility index value of each component that constitutes the multicomponent mixture;
An initial classification unit that classifies components having a melting point lower than a desired temperature among the components constituting the multi-component mixture as liquid phase components, and classifies components having a melting point equal to or higher than the desired temperature as non-liquid phase components. When,
A liquid phase calculation unit for estimating properties of the liquid phase,
The component information acquisition unit is
Composition information including the structure and fraction of each component of the multi-component mixture obtained by mass spectrometry of the multi-component mixture, and physical properties including the melting point and Hansen solubility index value of each component linked to the composition information get information and
The liquid phase calculation unit is
Calculate the average Hansen solubility index value of the entire liquid phase as a weighted average value obtained by weighting the Hansen solubility index value of each component classified as the liquid phase component by the volume fraction of each component in the liquid phase,
calculating the difference between the average Hansen Solubility Index value for the entire liquid phase and the Hansen Solubility Index value for each component in the non-liquid phase components;
Each component in the non-liquid phase component is reclassified as a liquid phase component or a non-liquid phase component based on the difference, and each component reclassified as a liquid phase component is incorporated from the non-liquid phase component to the liquid phase component. to update the liquid phase component and the non-liquid phase component,
Calculate the average Hansen solubility index value of the entire liquid phase after the update as a weighted average value obtained by weighting the Hansen solubility index value of each component in the liquid phase component after the update by the volume fraction of each component in the liquid phase,
Repeat updating the average Hansen Solubility Index values, the liquid phase components, and the non-liquid phase components until the final stage where there are no non-liquid phase components reclassified as liquid phase components;
An apparatus for estimating properties of a multi-component mixture, characterized by: Further comprising a non-liquid phase calculation unit for estimating properties of the non-liquid phase,
The non-liquid phase calculation unit calculates the aggregation degree of each component in the non-liquid phase component after updating in the final stage at the desired temperature, the average Hansen solubility index value of the entire liquid phase and the non-liquid phase component in the 26. The properties of the multi-component mixture according to claim 25, characterized in that it is calculated based on the difference between the Hansen solubility index value of each component and the concentration of each component in the non-liquid phase component after updating in the final stage estimation device. 27. A method of operating an apparatus according to claim 25 or 26, comprising:
13. A method of operating an apparatus relating to a multi-component mixture, characterized in that operating conditions are set based on the physical property values of the multi-component mixture estimated by the method according to claim 12. A computer program for causing the computer to perform the method according to any one of claims 1 to 21.

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