JP2019132740A - Estimation method of properties of multi-component mixtures - Google Patents

Abstract

To identify a molecular structure and abundance of each component constituting a multi-component mixture, based on a multi-component aggregation model using structural information and a physical properties database obtained therefrom and to provide a method of estimating properties of each component in the multi-component mixture.SOLUTION: In this method, mass spectrometry to a multi-component mixture is used to identify a molecular formula and its presence ratio of a molecule attributable for each of the resulting peaks. For each molecule, molecular formula is identified to determine a structure of a core constituting them, and further assigns it to determine the side chain and crosslinking. From the molecular structure of each component of the specified multi-component mixture, the melting point and the Hansen solubility index value of each component are obtained. A component of the components constituting the multi-component mixture having a melting point of less than a desired temperature is classified as a liquid phase component, and the components having the melting point of the desired temperature or more is classified as a non-liquid phase component.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for estimating properties of a multi-component mixture. More specifically, the present invention specifies the molecular structure of each component constituting a multi-component mixture by a computer, and based on a new multi-component aggregation model using the structural information and physical property value database obtained therefrom. The present invention relates to a method for quantitatively estimating properties such as dissolution, agglomeration and precipitation of various components in various multi-component mixtures including quality oil, a device used therefor, and a computer program for causing a computer to execute the method or device. .

In the operation of various equipment related to oil refining, the raw material oil is usually analyzed based on the overall physical properties such as specific gravity, viscosity, distillation properties (boiling point), and the operation results of oil types with similar past data are obtained. A method of determining operating conditions with reference is taken.
However, nowadays, imported crude oil types are diversified, and it is not easy to find similar past data. Furthermore, from the viewpoint of improving driving efficiency and environmental protection, it is no longer necessary to simply follow past driving records.
Therefore, rather than grasping the entire petroleum such as specific gravity, viscosity, and distillation properties as a whole, we grasp the chemical structure and the existence ratio at the level of the hydrocarbon molecules that make up the oil and It has been considered that if the driving conditions can be set based on the knowledge such as the estimated physical property value obtained, the driving can be performed more efficiently based on the objectivity. Therefore, in the oil industry, the advent of technology for grasping oil at a molecular level has been awaited.
However, petroleum is a mixture of a large number of hydrocarbon molecules, and especially heavy oil has a large molecular weight and a very large number of molecules having a complicated chemical structure. It was very difficult to identify the chemical structure and the ratio of their existence.

In the past, when analyzing petroleum at the molecular level and analyzing its chemical structure, techniques have been used to measure molecular weight with high accuracy using a mass spectrometer based on the Fourier transform ion cyclotron resonance method, which is a high-resolution mass spectrometer. It was. For example, it is the method described in Patent Document 1 or Patent Document 2.
In particular, Patent Document 2 discloses that a molecule constituting petroleum is collided with argon or the like, so that a cross-linked portion in the molecule is cut to be broken down into a core portion, and the chemical structure thereof is obtained. A molecular structure estimation method is described in which the original molecules are reconstructed by combining them later.

  Further, in the processing 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 the aggregation of asphaltenes, which are precursors of coke, in various situations including heavy oil cracking. For this reason, a solvent (solvent) that alleviates and suppresses asphaltene agglomeration is usually mixed with the raw material oil in advance. However, the type and amount of the solvent to be mixed are based on knowledge accumulated over many years. The current situation is that they are selected empirically.

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

Special table 2014-500506 gazette Special table 2014-503816 gazette Japanese Patent Laid-Open No. 2014-218643

  However, in the method described in Patent Document 2, it is determined based on the probability which part and which part to select and combine to form a molecule such as a core, a bridge, and a side chain. That's it. Therefore, even if the molecular structure of components is constructed in the same process based on certain mass spectrometry data, the results obtained are different for each construction work. That is, the method described in Patent Document 2 has a fatal defect that the constancy and reproducibility of the obtained results are not ensured and “the operational stability of the apparatus cannot be ensured”.

  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 value of the liquid phase component in the heavy oil, not the value of the solvent itself. . For this reason, of each component contained in heavy oil, which component dissolves to form a liquid phase, how the Hansen solubility index value of the liquid phase changes, and as a result, which component aggregates or It is important to know whether it precipitates. However, the properties of the liquid phase, aggregated phase and solid phase of a multi-component mixture, which is a solution composed of a plurality of components, and the mechanism of the phase change, particularly asphaltene dissolution, aggregation and precipitation in heavy oil, Despite being a major theme, little has been clarified.

  The present invention has been made under such circumstances, and by using a computer, the molecular structure and the existence ratio of each component constituting the multi-component mixture are specified with certain certainty, and the structural information and physical property values obtained therefrom are determined. It aims at providing the method of estimating the property of each component in a multi-component mixture based on the multi-component aggregation model using a database. Furthermore, this invention aims at providing the apparatus and program which are used for the property estimation method of the said multi-component mixture.

In order to achieve the above object, the present inventors have created the following present invention. That is, the method for estimating the property of a multi-component mixture according to the present invention is a method for estimating the property of a multi-component mixture by a computer,
(1) performing mass spectrometry on the multi-component mixture, for each of the obtained peaks, identifying the molecular formula of the molecule belonging to the peak, and further identifying the abundance ratio of the molecule;
(5) For each molecule whose molecular formula is specified in step (1), determining the structure of the core constituting the molecule, and further determining and assigning side chains and bridges;
(6) obtaining a melting point and a Hansen solubility index value of each component from the molecular structure of each component of the multicomponent mixture identified in the steps (1) and (5);
(7) Of each component constituting the multi-component mixture, a component having a melting point lower than a desired temperature is classified as a liquid phase component, and a component having a melting point higher than the desired temperature is classified as a non-liquid phase component. Steps,
(8) calculating an 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 a fraction in the liquid phase of each component; ,
(9) calculating the difference between the average Hansen solubility index value of the entire liquid phase and the Hansen solubility index value of each component in the non-liquid phase component;
(10) Based on the difference, each component in the non-liquid phase component is reclassified as a liquid phase component or a non-liquid phase component, and each component reclassified as a liquid phase component is converted from the non-liquid phase component to the liquid phase component. And renewing the liquid phase component and the non-liquid phase component;
(11) The average Hansen solubility index value of the entire updated liquid phase is calculated as a weighted average value obtained by weighting the Hansen solubility index value of each component in the updated liquid phase component by the fraction of each component in the liquid phase. Steps,
(12) repeating the steps (9) to (11) until a final stage in which the non-liquid phase component reclassified as the liquid phase component in the step (10) is eliminated.
It is characterized by this.

  In another embodiment of the present invention, a method for estimating a property value of a multi-component mixture, a method for processing a multi-component mixture, a property estimating device for a multi-component mixture, and a method for estimating a property of a multi-component mixture, and A method for operating the apparatus, a method for estimating the properties of a multi-component mixture, and a computer program for executing the apparatus are also provided.

  The processing method of the multi-component mixture of the present invention estimates the properties of the original multi-component mixture by the above-described property estimation method of the multi-component mixture, and further, based on the property estimation results, the original multi-component mixture of a desired type When the solvent is mixed in the desired fraction, when the temperature of the raw multi-component mixture is changed to the desired temperature, or in the raw multi-component mixture, the desired type of solvent is mixed in the desired fraction and the raw multi-component mixture Predict the properties of the new multi-component mixture when the temperature of the mixture is changed to the desired temperature, and based on the prediction, mix the desired type of solvent into the original multi-component mixture at the desired fraction, or Change the temperature of the multi-component mixture to its desired temperature, or mix the desired type of solvent into the original multi-component mixture in its desired fraction and change the temperature of the original multi-component mixture to its desired temperature It is characterized by that.

  According to the processing method for a multi-component mixture of the present invention, the property of the multi-component mixture can be predicted when a solvent is mixed in the multi-component mixture or the temperature of the multi-component mixture is changed. Based on this, it is possible to process a multi-component mixture.

  Also, in the method for treating a multi-component mixture of the present invention, preferably, the desired type of solvent and the desired fraction, and / or the desired temperature is estimated from the predicted properties of the new multi-component mixture. A solvent and a fraction in which all or a part of the aggregated phase component and the solid phase component are dissolved or the aggregation or precipitation of the aggregated phase component and the solid phase component is suppressed, and / or Or temperature.

  As a result, appropriate selection of the solvent species, addition of a new solvent, or measures to change the temperature of the solution are taken to dissolve all or part of the aggregated phase and solid phase in the solution, or the solute Aggregation or precipitation can be suppressed.

  According to the present invention, the molecular structure and the abundance ratio of each component constituting a multi-component mixture are specified with a certain degree of certainty using a computer, and the physical property data associated with the structural information obtained therefrom is used. A component aggregation model can provide a method for estimating the properties of a multi-component mixture.

6 is a flowchart illustrating a method according to an embodiment of the present invention. It is a schematic diagram explaining collision induced dissociation. It is a JACD display example of a molecule belonging to a mass spectrum obtained by FT-ICR-mass spectrometry and a certain peak. It is a chart of a mass spectrum obtained by FT-ICR-mass spectrometry. It is a schematic diagram explaining comparison by comparing m / z of a peak obtained in FT-ICR-mass spectrometry after collision-induced dissociation with an accurate mass in a core structure list. The upper row is a chart of mass spectrum obtained by FT-ICR-mass spectrometry for a multi-component mixture as a sample, and the middle and lower rows are the molecular formulas attributed to the obtained peaks and the types and numbers of heteroatoms. It is a chart that is divided into “groups” for each and further re-peaked by the DBE value in the “groups”. It is a schematic diagram explaining the presence rate of a multi-core. It is a schematic diagram explaining the presence rate of a single core. It is a schematic diagram of the core originating in DBE value 22. It is a schematic diagram of a core derived from a DBE value of 20. It is a schematic diagram explaining the "class" division of the core for every DBE value. It is a schematic diagram showing what is arranged in the order of the mass of the parent from which the “class” of the core for each DBE value is derived. In the said FIG. 12, it is a schematic diagram explaining allocation of a core. It is a chart of the mass spectrum obtained by FT-ICR-mass spectrometry about polycyclic aromatic resin (PA). It is a chart of a mass spectrum obtained by FT-ICR-mass spectrometry after collision induction dissociation about polycyclic aromatic resin (PA). It is a schematic diagram of an HSP value. It is a graph showing the amount of the liquid phase of the model heavy oil without a solvent, the aggregation phase, and the solid phase, and the average aggregation degree of an aggregation phase. It is a graph showing the amount of the liquid phase of the model heavy oil in a toluene solvent, the aggregation phase, and the amount of a solid phase, and the average aggregation degree of an aggregation phase. It is a functional block diagram of the property estimation apparatus of the multicomponent mixture by embodiment of this invention. It is a graph showing the amount of liquid phases, agglomerated phases and solid phases of model heavy oil in an equal mass mixed solvent of toluene and bromobenzene, and the average agglomeration degree of the agglomerated phases. It is a functional block diagram of the property estimation apparatus of the multicomponent mixture by embodiment of this invention.

<Definition>
In describing embodiments of the present invention, first, terms and expressions used in this specification will be described.
(1) "Multi-component mixture"
A “multi-component mixture” is a concept that encompasses any mixture of two or more components. The content ratio of the components is not limited. Specifically, “petroleum” is preferable, and “heavy oil” is more preferable. More specifically, it is a “mixture containing many aromatic compounds as main components”.

(2) “Ingredients”
“Component” means “a mass of a mixture based on a specific physical or chemical property”, that is, “a fraction (fraction) fractionated based on a specific physical or chemical property. ) ". Examples of a method for bundling a specific physical or chemical property as a standard include a method of specifying a boiling range in a distillation test and fractionating a component in the temperature range as one component. In this case, the mixture is referred to as “an aggregate of fractions (fractions)”. Alternatively, the “component” may be regarded as “a collection of molecules recognized as belonging to the same molecular species”, each of which constitutes a multi-component mixture. Here, “same” means “specifies the molecular structure perfectly and is the same” or “isomers on the molecular structure (same molecular formula but different structure)” For example, it may be understood as the meaning of “same in a structure specified by a method such as JACD” to be described later. Furthermore, it may be broadly understood as meaning “a collection of molecules collectively based on an arbitrarily defined standard”.

(3) “Configure”
“Composing a multi-component mixture” does not have to 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, depending on how detailed it is necessary to specify the molecular species as a component, “each component to be configured” is determined appropriately. do it. For example, only a molecular species having a certain abundance (existence ratio) or more in a multi-component mixture may be regarded as a “constituent component”. The necessity of identifying the molecular structure for all of a huge variety of molecular species such as petroleum is not necessarily high, and molecular species having only a trace amount 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”
“Fraction” may be anything as long as it shows an abundance such as mass fraction, volume fraction, or mole fraction, and is a concept that includes all of them. When calculating the average Hansen solubility index value of the entire liquid phase, a 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 all actions as long as it is an action to specify any information related to the structure of the molecule regarding the “molecule” in the “component”. Depending on the purpose and necessity, the degree and display method may be appropriately selected. In addition to the act of specifying the structure of the entire molecule, information on the structure of a part of the molecule may be incorporated. For example, only the structure of the core part may be specified, and the side chain part and the cross-linked part may be left in the molecular formula without specifying the structure.
In the present 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 bonding positions of attributes, which will be described later. In the present specification, “molecule” may be regarded as a concept including all isomers.

(6) “Identify the proportion of each component”
“Specifying the abundance ratio of each component” includes all acts as long as it is an act of identifying the ratio of each component constituting the mixture. In addition, it does not mean that the existence ratio must be specified for all the component types that make up the mixture, but includes components that are present only in amounts that are difficult to detect by analytical techniques and components that do not need to be specified. It is not the case that “the existence ratio of each component is specified” until the existence ratios of all the components are specified. Such trace components may be collectively handled as “other components”. Furthermore, these may be excluded from the range of “each component constituting the mixture” and may not be included in the denominator in calculating the abundance ratio of other components.

(7) "All"
In the present specification, “all” does not necessarily mean “100% all”. For example, the term “all peaks” in the mass spectrum is literally related to not only the meaning of “100% of all peaks” but also, for example, molecules that are not necessarily required for the purpose of study in that scene. Peaks and peaks that are difficult to distinguish may be regarded as meaning that other peaks are excluded after appropriate exclusion.

(8) “Peak”
The horizontal axis of the peak obtained in mass spectrometry is m / z for the molecular ion or pseudo-molecular ion of each component constituting the multicomponent mixture. Since the numerical value indicated by m / z is a numerical value corresponding to the mass of the molecular ion or the pseudo-molecular ion, it generally represents the molecular weight of the molecule assigned to the peak. In the present 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”. Further, the height of the peak indicates the relative existence ratio of molecules belonging to the peak.

(9) "Molecular formula"
“Molecular formula” refers to a formula that indicates only the type and number of elements constituting a molecule, and the structure is not specified. Since the type and number 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 Fourier transform ion cyclotron resonance method mainly used in the present invention (hereinafter also referred to as “FT-ICR-mass spectrometry”, a spectrum obtained by FT-ICR-mass spectrometry is referred to as “FT-ICR-mass spectrometry spectrum”. ”), The value of m / z can be determined up to the fourth decimal place. Therefore, the molecular formula of the molecule belonging to the peak can be determined by performing precise mass number matching that also considers the presence of atomic isotopes. Since the molecular formula merely represents the type and number of elements constituting the molecule, a plurality of isomers may exist as the molecule corresponding to the determined molecular formula. That is, a plurality of isomers having the same molecular formula can belong to one peak.
However, due to the characteristics of FT-ICR-mass spectrometry, even if the molecular formula is the same, the mass is different from the original molecular ion due to, for example, the addition of a hydrogen ion to the molecular ion. May appear as a peak. Therefore, even if the peak appears as another peak in the measurement, the same type and number of elements constituting the molecular formula may be regarded as “the same molecular formula”. In the term “molecule corresponding to the molecular formula”, “the molecular formula” may be understood as meaning “the same molecular formula”. In addition, the term “a certain peak” may be considered as a concept in which all the various m / z peaks that are said to represent “the same molecular formula” in the above sense are collectively regarded.

(10) "Core", "Single core", "Double core"
“Core” is a kind of “attribute” described in the section “JACD” to be described later. Specifically, an aromatic ring or a naphthene ring itself, or an aromatic ring and a naphthene ring are directly bonded rather than bridged. In which a heterocycle is directly bonded to an aromatic ring or naphthene ring, not a bridge. Since the crosslink or side chain is an attribute different from the core, “core” means one having no crosslink or side chain.
On the other hand, “single core” is a concept indicating a molecule having only one core. Since it is a concept that refers to a molecule, it includes those in which a side chain is bound to the core. A molecule formed by crosslinking two or more of the cores is referred to as “multi-core”. Since “multi-core” also means a molecule, it includes those in which a side chain is bound to the core. A molecule formed by crosslinking two cores is called a “double core”.
For example, since the naphthalene molecule shown below consists of one aromatic ring, it is a “single core” and 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 “C _c H _h N _n O _o S _s ”.
DBE = c−h / 2 + n / 2 + 1 (1)
(In the formula, c represents the number of carbon atoms, h represents the number of hydrogen atoms, n represents the number of nitrogen atoms, o represents the number of oxygen atoms, and s represents 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 related to the molecular structure, and displays the molecular structure by the type of attribute and the number of attributes. It doesn't show in which position the attribute is combined.
In the above, “attribute” is a concept indicating a part (part) on a chemical structure constituting a molecule. In the aromatic compound, specifically, it refers to the aforementioned “core”, “bridge”, and “side chain”.
According to this display method, the structure of each of the enormous number of molecules constituting oil can be specified to a necessary and sufficient extent.
Description will be made by taking a molecule represented by the following chemical formula as an example.

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

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

(13) “Property value”
“Physical property value” is a value obtained based on the molecular structure specified by the above method and its abundance ratio, as long as it expresses the physical or chemical properties, properties and characteristics of the substance. Regardless of the name, it is included in the “physical property value”. In the present specification, the “physical property value” is not limited to these, but, for example, melting point, Hansen solubility index value, Gibbs free energy generated, 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, generated heat, heat capacity, dipole moment, enthalpy, entropy, etc.

(14) "Oil"
In this specification, “petroleum” means crude oil, fractions obtained by distilling crude oil, fractions obtained by subjecting various fractions to treatment by secondary equipment such as reforming and decomposition, and the like. A generic concept that includes Alternatively, a fraction obtained by distilling crude oil may be a fraction obtained by further fractionating into components such as saturated hydrocarbons and aromatic hydrocarbons.
(15) "Equipment related to petroleum"
In the present specification, the “equipment relating to petroleum” includes all devices relating to petroleum processing such as distillation devices and extraction devices, devices involving chemical reactions such as reforming devices, hydrogenation reaction devices, and desulfurization devices. “Petroleum equipment” is generally referred to as “petroleum refining equipment”.

<Identification of molecular structure of each component of multi-component mixture>
Next, each step for specifying the molecular structure of each component of the multi-component mixture in the present embodiment will be described with reference to the flowchart of FIG.
(1) Step 1 (mass spectrometry) (S1 in FIG. 1)
Step 1 is a step in which mass analysis is performed on the multi-component mixture, and for each of the obtained peaks, the molecular formula of the molecule belonging to the peak is specified, and the abundance ratio of the molecule is specified. That is, it is a step of performing mass spectrometry on a multi-component mixture, specifying the molecular formula of the molecule belonging to each peak for all the obtained peaks, and further specifying the abundance ratio of molecules corresponding to the molecular formula. .

  For mass spectrometry, it is preferable to use an ultra-high resolution mass spectrometer. Specifically, high-precision measurement is performed using a FT-ICR-mass spectrometer by a known method, that is, by soft ionizing a sample to form molecular ions or pseudo-molecular ions.

(2) Step 2 (collision-induced dissociation) (S2 in FIG. 1)
Step 2 is a step of performing collision-induced dissociation on the multi-component mixture. “Collision Induced Dissociation (hereinafter also referred to as“ CID ”)” refers to an operation in which molecules are ionized and collided with an inert gas such as argon to break crosslinks and side chains. Usually, it is preferable to give collision energy so that the bridge | crosslinking and side chain in each component which comprise the said multicomponent mixture are cut | disconnected. Fragment ions for each core are generated by breaking the crosslinks and side chains. This core may have an aliphatic group having about 0 to 4 carbon atoms as a side chain that could not be cleaved by collision-induced dissociation.
When FT-ICR-mass spectrometry is performed on a multi-component mixture, the molecular formula of the molecule constituting the multi-component mixture can be determined from the m / z of the peak obtained. Information on the “core” of the molecule Cannot be obtained. Therefore, by further performing collision-induced dissociation and cutting the crosslinks and side chains in each molecule constituting the multicomponent mixture, it is possible to know the types of cores present in the entire multicomponent mixture.
As conditions for performing the collision-induced dissociation, collision energy capable of effectively cleaving crosslinks and side chains in the molecule, for example, 10 to 50 kcal / mol is preferable, and 20 to 40 kcal / mol is more preferable. Note that 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 in which mass analysis, preferably FT-ICR-mass analysis, is performed on each fragment ion generated by collision-induced dissociation in Step 2 to specify the structure and abundance ratio of the core constituting each fragment ion. is there.

(A) First, a method for specifying the structure of the core constituting each fragment ion will be described.
Specifically, this is a method of collating the information about the core obtained in the step 2 with the information about the core described in the core structure list prepared in advance to identify the structure of each core.
Details are as follows.
i. Acquisition of information about the core after collision-induced dissociation In FT-ICR-mass analysis of each fragment ion after collision-induced dissociation, the core portion is the same, but the number of carbons is about 0 to 4 as a side chain. The fragment ions having an aliphatic group of 1 have different masses depending on the type of their side chains, and thus appear as separate peaks. Therefore, for those having an aliphatic group having 0 to 4 carbon atoms as a side chain in the core, these various masses are calculated in advance, and if the different peaks appearing above are compared and compared, the mass of the core itself Can be determined.
Using this method, in step 2, for each of the peaks obtained after collision-induced dissociation, the core attributed to that peak has a mass and how many heteroatoms such as O, N or S atoms exist. In addition, information on how many aromatic rings are present can be obtained from the DBE value.

ii. Identification of the core structure after collision-induced dissociation As a method for identifying the core structure after collision-induced dissociation, various cores that can be assumed to constitute each component molecule of the multi-component mixture were listed as models in advance. Create a “core structure list” and collate the information such as the molecular weight of the core and the type and number of heteroatoms stored in the list with the core information obtained above. There is a method of selecting a core model that is considered to be the most appropriate from the above and assigning that core as the core.
By this method, the core is assigned to all the peaks obtained by FT-ICR-mass spectrometry after collision-induced dissociation, and the structure can be known.

iii. Core structure list The type of core stored in the core structure list is not particularly limited and may be any type. However, the validity of the selection of the core to be stored depends on the structure of each core. 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 as a sample. For example, when the multi-component mixture is petroleum, a “core structure list for identifying the molecular structure of petroleum” may be prepared in advance based on knowledge of petroleum so far.
In creating the list, the number of basic aromatic rings, the type and number of naphthene rings directly bonded to the aromatic ring (including the difference between the 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 in what form the naphthenic ring is bonded to which position of the core.
For example, the size of the aromatic ring is limited to 6 rings, the heteroatoms are assumed to be N, O, S, and the number of heterocycles is about 10 in consideration of computational convenience. Create a list.

iv. Selection from Core Structure List There may be a plurality of core structure lists that have the same molecular weight, DBE value, and heteroatom type and number, but different structural formulas. In this case, a rule may be appropriately determined as to which of the plurality is selected as the first priority. For example, the following 1-3 are mentioned as priority.
1. Preference is given to those consisting only of aromatic rings.
2. Priority is given to those with many unsaturated bonds.
3. Priority is given to those with less rings.

(A) 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 the core having the mass can be obtained.
The structure of each core after the collision-induced dissociation obtained in Step 3 will be used later in Step 5, and the existence ratio of each core after the collision-induced dissociation is used later in Step 4. It will be.

(4) Step 4 (Estimation of the existence mode and existence ratio of cores for each class) (S4 in FIG. 1)
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 for all molecules belonging to each “class”. This is a step of estimating the existence mode and the existence ratio.
In other words, the molecules belonging to all the peaks in step 1 are assigned to “class” based on “type and number of heteroatoms (including zero) and DBE value” in each molecular formula specified in step 1. This is a step of estimating the existence mode and the existence ratio of all molecules belonging to each “class”.

Hereinafter, step 4 will be described in detail.
(A) In Step 1, since the molecular formulas are specified for all the peaks, the types and numbers of heteroatoms and the DBE values in the molecular formulas are found. Therefore, in this step, based on this “type and number of heteroatoms and DBE value”, each molecule assigned to all peaks is grouped by “type and number of heteroatoms and DBE value”. Transfer into each “class”.
The “type and number of heteroatoms” is specifically “the number of heteroatoms for each heteroatom type”. Since the hetero atom is preferably a nitrogen atom, a sulfur atom and an oxygen atom, the “type and number of hetero atoms” preferably means “the number of each of the nitrogen atom, sulfur atom and oxygen atom”. You can also. Therefore, in terms of heteroatoms, “the ones in which the number of nitrogen atoms, the number of sulfur atoms, and the number of oxygen atoms all match” belong to the same “class”.

(B) Next, in each class enclosed by “type and number of heteroatoms and DBE value” described in (a), it is estimated what single core or multi-core each molecule belonging to that class is. . In addition, it is estimated what ratio each of the single core and the multi-core exists.
In making these estimations, it is preferable to make some assumptions for the convenience of actual calculation.
Here, “multi-core” can have various combinations depending on what cores are cross-linked and bonded. However, the sum of the DBE values of a plurality of cores forming the multi-core and the sum of the numbers corresponding to the types of heteroatoms are the same for all members belonging to the class.

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

  When the molecule belonging to the class is a single core, the type and number of heteroatoms corresponding to the class and the single core having the DBE value are applicable. When the molecule belonging to the class is a multi-core, the sum of the numbers of the same kind of heteroatoms present in the plurality of cores constituting the multi-core and the sum of the DBE values of the plurality of cores are A combination of cores so as to match the type and number of heteroatoms of the class and the DBE value is applicable. Since the sum of the numbers and the sum of the DBE values according to the types of heteroatoms of the plurality of cores only needs to correspond to the types and numbers of the heteroatoms of that class and the DBE value, the combination of the plurality of cores constituting the multicore In general, the number is not limited to one.

(D) Next, it is estimated what ratio each single-core and multi-core molecules that belong to the class exist.
Preferably, first, it is assumed that the existence ratio of the multi-core is a product of the existence ratios of a plurality of cores constituting the multi-core, and this is an estimated value.

(5) Step 5 (determination of core structure, side chain, and crosslinking) (S5 in FIG. 1)
Step 5 is a step of determining the structure of the core constituting each molecule, the side chain and the bridge being determined and assigning to each molecule whose presence mode is estimated in Step 4.

(A) “Determining the structure of the core that forms them” is performed by the following operations iv with respect to “each molecule whose existence mode is estimated in step 4”.
i. In the case of a multi-core whose presence mode is estimated in step 4, it is divided (released) for each core constituting it.

  ii. For all of the cores that are estimated to be single-core in step 4 and the cores generated by releasing multi-core as in i above, the same “type and number of heteroatoms and DBE value” Re-categorized into each "class". Incidentally, the “class” here is a concept related to the core obtained by releasing the original single core and multi-core, and is different from the “class” related to the molecule described in step 4.

  iii. For all “classes” of “type and number of heteroatoms and DBE value” enumerated in ii above, a specific structure is assigned to all of the cores existing in the “class”.

(A) Further, side chains and crosslinks are determined by the following operations i to iii.
i. Although the structure of the core part of the single core or the multi-core was able to be specified by the above, the target sample was obtained by FT-ICR-mass spectrometry only by assuming the existence of only the core part. The m / z of the peak produced does not match the mass. That is, even if the masses based on carbon, hydrogen, and heteroatoms involved in the core portion are summed, a difference from the mass indicated by m / z of the peak obtained by FT-ICR-mass spectrometry occurs.
Therefore, the difference in mass is considered to be derived from the presence of the side chain bonded to the core and the bridge connecting the cores, and the number of carbons and the number of hydrogen are determined so that the difference is eliminated, Assign it to the core as side chains and bridges.
For example, it is assumed that a certain double core formed by crosslinking the core 1 and the core 2 is assigned to a certain peak of m / z = n by the above procedure. At this time,
Difference in mass (d) = n− (mass of core 1 + mass of core 2)
Is derived from the presence of side chains and crosslinks.

ii. In the above i, the number of carbons and the number of hydrogens to be allocated as side chains and bridges are determined, but the structure of the side chains and bridges has not been determined yet. Therefore, in estimating what type of side chains and bridges correspond, for example, the following rules are decided in consideration of the existence probability of combinations of assumed side chains and bridges. It may be estimated. As a rule, conditions such as the upper limit of the number of carbons constituting the side chain or the bridge and the number of side chains may be determined in advance.
iii. In the above i, when there is no side chain or bridge corresponding to the difference in mass, a structure in which the core 1 and the core 2 are simply bonded may be applied.
(C) “Assigning the side chain and the bridge determined above to the core” does not mean to determine which position of which core the side chain and the bridge are bonded to.

  (D) In this way, for each single core or double core whose existence mode is estimated in step 4, the structure of the core constituting them is determined in step 5, and the side chain and the bridge are further determined. it can.

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

  In the present invention, the multi-component mixture may be one fraction obtained by fractionating a multi-component mixture into two or more arbitrary portions. That is, when the “multicomponent mixture” in the above is regarded as one fraction I obtained by fractionating the large bundle “multicomponent mixture A”, the “multicomponent mixture A” It can be regarded as a mixture of fractions such as I, fraction II, etc. For the fraction II, the molecular structure of each component constituting the fraction II can be specified by the same method as that used for the fraction I.

In performing the fractionation, there is no particular limitation on the standard used as the boundary of the fraction or the method for fractionation. Specifically, the following method is preferable.
This is a method in which a multi-component mixture is subjected to high-precision type separation pretreatment and fractionated into a plurality of components. In particular, in the case of heavy oil, it is preferable to perform such fractionation. The method of “separation pretreatment by type” is not particularly limited, and may be separated into several components according to an arbitrary standard. However, a column chromatography fractionation method, a Soxhlet extraction method, or a high-speed solvent extraction method may be used. A known method such as a solvent extraction method may be used. In the case of heavy oil, it is preferable to use a column chromatographic fractionation method, such as the method described in JP2011-133363A. The number of components to be fractionated may be appropriately selected according to the purpose.

Specifically, a method including the following first to third steps is exemplified.
(First step)
The heavy oil is separated into a martens component soluble in n-paraffin and other insoluble components.
(Second step)
Using the column chromatography, the marten component separated in the above (first step) is saturated (Sa), one ring aromatic component (1A), two ring aromatic component (2A), three or more ring aromatic components ( 3A +), polar resin component (Po), and polycyclic aromatic resin (PA).
(Third step)
More preferably, the tricyclic or higher aromatic fraction (3A +) obtained in the second step is further separated by using preparative liquid chromatography, and the Peri type 4-ring aromatic fraction and the Cat-type 4-ring aromatic fraction. May be separated into five or more aromatic components (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 is a step A for fractionating a 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 above method. Step B for identifying the structure and abundance ratio, and Step C for integrating the molecular structures and abundance ratios of all components obtained for all the fractions according to the mixing ratio of each fraction fractionated in Step A. It is the method characterized by including.
As described above, “multi-component mixture A” is regarded as a mixture of fractions obtained by fractionating it, such as fraction I, fraction II,. With respect to the fraction, the molecular structure of each component constituting the fraction and the abundance ratio thereof are specified by the above-described method. Thereafter, all components of all fractions are combined according to the mixing ratio of fraction I, fraction II in each of “multi-component mixture A”, that is, the fraction yield. With respect to the entire composition model of “A”, it is possible to specify what component is used and what proportion.

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

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

  The physical property values registered in the database are melting point, Hansen solubility index value, boiling point, critical humidity, critical pressure, critical volume, vapor pressure, liquid density, gas viscosity, liquid viscosity, surface tension, dipole moment, polarizability. About 200 kinds of physical properties such as ionization potential, heat of formation, enthalpy, entropy, free energy, heat capacity and the like.

These physical property values are usually calculated using an atomic group contribution method or a molecular orbital method. In the group contribution method, the physical properties of a substance are determined by specifying the chemical structure of the substance, and based on the unique parameter values of the various atomic groups that exist, that is, the “group”. This is a method of calculating the physical property value. That is, it is assumed that the “group” of the substance is specified. In the molecular orbital method, it is premised that the “group” of the substance is first identified and the structure is identified based on the identified “group”.
In the present invention, as described above, for each component constituting the multi-component mixture, the various atomic groups present are specified. The physical property value can be calculated. Furthermore, since the existence ratio of each component is also specified, the physical property value of the entire multi-component mixture can be appropriately estimated from the physical property values of each component, taking this existence ratio into consideration.

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

  Prior to the description of the embodiments of the present invention, a multi-component aggregation model (MCAM) based on the present invention will be described by the following steps (7) to (16).

(7) Step 7 (Separation into liquid phase component and non-liquid phase component) (S7 in FIG. 1)
In the above steps (1) to (6), the fraction, melting point and Hansen solubility index value of each component are obtained, and a desired temperature T is set.
Among the components constituting the multi-component mixture, components having a melting point lower than the desired temperature T are classified as liquid phase components, and components 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 the liquid phase component in step (7), the 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. For each component, the volume fraction can be calculated by acquiring in advance various information relating to physical properties such as density and molecular weight.

(9) Step 9 (calculation of difference in HSP value between the entire liquid phase and each non-liquid phase component) (S9 in FIG. 1)
The 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 of the 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 non-liquid. The liquid phase component and the non-liquid phase component are updated by incorporating the phase component into the liquid phase component.
The reclassification update 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 the average HSP value of the entire liquid phase after update) (S11 in FIG. 1)
For the HSP value of each component in the liquid phase component updated in step (10), the weighted average value weighted by the volume fraction in the updated liquid phase of each component is the average HSP of the entire liquid phase after update. Calculate as a value.

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

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

(14) Step 14 (classification of non-liquid phase components based on the degree of aggregation) (S14 in FIG. 1)
Based on the degree of aggregation D, each component in the updated non-liquid phase component is classified into an aggregated phase component and a solid phase component.

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

(16) Step 16 (Output of properties of multi-component mixture) (S16 in FIG. 1)
Based on the information obtained from the above steps, the properties of the multi-component mixture are output.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Identification of molecular structure of each component of multi-component mixture>
The method for estimating the properties of a multi-component mixture according to the present invention will be described by applying each step shown in the flowchart of FIG. 1 to an assumed model. As the “multicomponent 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 abundance ratio of molecules corresponding to the molecular formula are specified. For example, when the spectrum chart obtained by FT-ICR-mass spectrometry in FIG. 4 is viewed, many peaks appear when the mass (m / z) is around 303.2. For each of the peaks, identify the molecular formula of the molecule to which it belongs.
In addition, the ratio of the height of a certain peak to the total sum of the heights of all peaks represents the proportion of molecules belonging to that peak, so the proportion of molecules corresponding to the molecular formula of each component is specified from that height. To do.

(2) Step 2 (collision-induced dissociation (CID)) (S2 in FIG. 1)
In step 2, collision-induced dissociation is performed on the multicomponent mixture.
As shown in FIG. 2, the parent ion having 40 carbon atoms and DBE = 17 is cleaved by side-chain and bridge by collision-induced dissociation to dissociate into two fragment ions. 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 are equal.
By CID, as shown in FIG. 2, most of the molecules with crosslinks are cleaved and cleaved, and under appropriate conditions, they will consist of a core and side chains with 4 or less carbon atoms at most.

(3) Step 3 (identification of structure and existence ratio of each core) (S3 in FIG. 1)
In step 3, FT-ICR-mass analysis is performed on each fragment ion generated by the CID in step 2, and the structure and the existence ratio of the core constituting each fragment ion are specified. That is, for the peak obtained by FT-ICR-mass spectrometry for each fragment ion after CID, the core structure and the existing ratio belonging to it are specified.
With reference to the schematic diagram of FIG. 5, the structure of each core and the method for specifying the existence ratio will be described. Here, the core is attributed to each peak by comparing and collating the m / z value of the FT-ICR-mass spectrum after CID with the accurate mass of the core stored in the core structure list. At that time, the cores stored 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 all the peaks in the FT-ICR-mass spectrum after CID, the assigned core structure, molecular weight, type and number of heteroatoms, and DBE value are specified.
The existence ratio of the core assigned to each peak can be determined from the relative height of the assigned peak.

(4) Step 4 (Estimation of the existence mode 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 “class”. The existence mode and the existence ratio are estimated for all molecules.
(A) First, the peaks obtained by FT-ICR-mass spectrometry of the target multicomponent mixture are summarized for each “class” of “type and number of heteroatoms and DBE value” as follows. And expressed as a peak.
This will be described with reference to FIG. The upper part of FIG. 6 shows “peaks obtained by FT-ICR-mass spectrometry”. In the peak obtained by FT-ICR-mass spectrometry, the molecular formula of the molecule belonging to the peak, the type and number of heteroatoms, and the DBE value are known. Therefore, as shown in the middle of FIG. 6, among all the molecules assigned to all the peaks, the molecules having no heteroatoms in the molecular formula are first bundled as a “group of zero heteroatoms”. In addition, all the molecules that are supposed to exist in the “group of zero heteroatoms” are divided into peaks for each “DBE value”. Next, as shown in the lower row, molecules having one nitrogen atom in the molecular formula are bundled as “group of N atom = 1” and then exist in “group of N atom = 1”. For all the molecules that became, each “DBE value” is divided into peaks. In this way, for all the “groups of types and numbers of heteroatoms”, the corresponding molecules are bundled, and all molecules existing in the group are divided and peaked for each “DBE value”.

In the above, the “group of zero heteroatoms” has been described, but in the case of a molecule in which only one nitrogen atom exists as a heteroatom in the molecular formula, these are bundled as “N1 molecular group” and all belong to it Are divided into “classes” for each “DBE value”. For example, “classes” collected with DBE values of 22 are classified as “N1 molecule group DBE values of 22 classes”. Further, in the case of a molecule in which one nitrogen atom and one sulfur atom exist as heteroatoms in the molecular formula, they are bundled as another group called “N1S1 molecular group”. Furthermore, molecules having the same “type and number of heteroatoms and DBE value” are classified into the “same class” even if the molecular formulas are different because the numbers of carbon and hydrogen are different.
As described above, a group of molecules bundled in a unit of “class” can be expressed as a peak.

(B) Next, for each “DBE value peak” in each group of “type and number of heteroatoms”, it is estimated what core the peak is composed of.
In this case, it is preferable to make some assumptions for practical calculation. Hereinafter, “DBE value = 22” will be described as an example.
When the DBE value is 22, examples of the core to be listed include a single core having a DBE value of 22 and a multi-core including a plurality of cores having a sum of DBE values of 22.
Here, assumption (1) is set as follows.
Assumption (1): “All multi-cores are composed of two cores, ie, only double cores.”
Therefore, in the case of DBE = 22, the single core is composed of one core of DBE = 22, and the double core is based on the above assumption (1), and two assumed cores (here, “core A and core B”). “)” Are as shown in Table 2 below.

In addition, when the result of FT-ICR-mass analysis after CID is seen, it can be said that there is no core having a DBE value of 1 to 5, and a core having a DBE value = 1 to 5 need not be considered. Therefore, the combination of the 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, it is estimated what ratio each core exists.
In this estimation, the following assumption (2) and assumption (3) are set and determined separately for i. Double core (multi-core) and ii. Single core.

i. In the case of a double core, assumption (2) is set as follows.
Assumption (2): Among the double cores consisting of a combination of two cores whose sum of DBE values is 22, for example, “the existence ratio of the double cores consisting of the cores with DBE value 12 and the cores with DBE value 10 is DBE after CID It is assumed that this is the product of the presence ratio of the core having a value of 12 and the presence ratio of the core having a DBE value of 10, and this value is used as the estimated value. FIG. 7 schematically shows the existence ratio of double cores based on assumption (2).
Here, the existence ratio of the cores having the DBE value 12 after CID is the ratio of the peak height of the DBE value 12 to the sum of the peak heights of all the DBE values.
That is, the ratio of peaks having a DBE value of 12 is (total peak height for molecules having a DBE value of 12 after CID) / (total height of all peaks after CID).
The same is true for the existence ratio of the DBE value of 10.
In the same manner, the existence ratio of a double core composed of other combinations of two cores with a sum of DBE values of 22, such as a core with a DBE value of 14 and a core with a DBE value of 8, can be estimated. .

ii. In the case of a single core, the assumption (3) is set as follows.
Assumption (3): The existence ratio of single cores having a DBE value of 22 is assumed to be “a value obtained by dividing the existence ratio of the peak of the DBE value 22 after CID by the DBE value 22”. Then, this divided value is set as an estimated value. FIG. 8 schematically shows the existence ratio of single cores based on assumption (3).
As described above, it is possible to estimate the existence ratio of single cores and various double cores having a DBE value of 22.

In the above description, the case of “hetero atom = DBE value in zero group = 22” has been described, but among the target multi-component mixture, when hetero atom = zero, DBE value = 13 to 32 exists ( Therefore, for each DBE value, the existence state of the core belonging to it is similarly estimated.
Further, in the case of N = 1, in the case of N = 2, the above operation is performed for each group of “type and number of heteroatoms”. In such a case, in the multi-core, the number of types of cores that can be taken is enormous depending on where the hetero atom exists. Therefore, for example, an assumption may be made that “the hetero atom does not exist in the side chain and the bridging portion but exists only in the core”. In addition, in the case where there are many heteroatoms, for example, “a group in which one nitrogen atom and one sulfur atom exist (N1S1 group)”, “nitrogen is bonded to one of two cores bonded by a bridge. An assumption may be made that there is one atom and one sulfur atom on the other.
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 what ratio each single-core and multi-core molecules that belong to the class exist. Preferably, first, it is assumed that the existence ratio of the multi-core is a product of the existence ratios of a plurality of cores constituting the multi-core, and this is an estimated value.

  In the above example, among the double cores from the combination of two cores with the sum of the DBE values of 22, for example, the existence ratio of the double cores having the DBE value 12 core and the DBE value 10 core is “DBE after CID”. It is assumed that the product is the product of the presence ratio of the core having the value 12 and the presence ratio of the core having the DBE value 10 and this is assumed to be an estimated value.

Here, the existence ratio of the core of the DBE value 12 after the CID is the ratio of the peak height of the DBE value 12 after the CID to the total sum of the heights of all the peaks after the CID. It can be calculated by using a known value. In addition, the existence ratio of those having a DBE value of 10 can be known in the same manner. Further, the double core existence ratio can be estimated in the same manner for a double core composed of another combination in which the sum of the DBE values is 22, for example, a core having a DBE value of 13 and a core having a DBE value of 9.
In this way, even if the class and number of heteroatoms and the DBE value are regrouped for each “class” consisting of molecules, it is possible to estimate the abundance of various multicores belonging to that class. it can.

Further, as the following assumption, it is assumed that the existence ratio of the single core having a DBE value of 22 is a value obtained by dividing the existence ratio of the peak of the DBE value 22 after CID by the DBE value “22”. Is preferable.
Assuming the above, it is possible to estimate the existence ratio of single cores and various multi-cores having a DBE value of 22.

(5) Step 5 (determination of core structure, side chain, and bridge) (S5 in FIG. 1)
In step 5, the structure of the core constituting them is determined for each molecule whose presence mode is estimated in step 4, and further, side chains and bridges are determined and assigned.
(A) First, for each molecule whose presence mode is estimated in step 4, the structure of the core constituting them is determined and assigned. Specifically, it is as follows.

(A-1) “Preparation”
According to the following procedures i to v, all “cores” are grouped into “classes” for the same “type and number of heteroatoms and DBE value”.
i. In the case of the double core whose presence mode is estimated in step 4, this is temporarily canceled and divided into the cores that are configured. In other words, not only the original single core, but all cores generated by releasing the double core are regarded as independent.
For example, in the above example, as shown in FIG. 9, when the DBE value = 22, the DBE value is 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 22 Will be divided into cores. (In the previous example, the FT-ICR-mass analysis results after CID did not include cores with DBE values of 1-5, so it is necessary to consider cores with DBE values = 1-5 And can be excluded.)
For other DBE values, the double core is canceled and divided for each core.
As shown in FIG. 10, for example, when DBE value = 20, the DBE value is divided into 6, 7, 8, 9, 10, 11, 12, 13, 14, and 20 cores as in the case of 22. It will be.

ii. Next, all the cores generated from the original single core and the released double core are summarized for each DBE value. For example, those having a DBE value of 10 collect all DBE values = 10 generated by the release regardless of the original double core. All DBE values are collected in the same manner, such as 12.
At this time, as shown in FIG. 11, each collected as “DBE value = 10” has a different abundance depending on its origin. The abundance of the parent of origin (that is, whether the parent is of DBE value = 10 derived from the DBE value = 22, or the parent is of DBE value = 10 derived from the DBE value = 20) It is proportional.

  iii. Furthermore, even when “no hetero atom. DBE value = 10” and “the DBE value of the parent from which the parent is derived is the same 22”, the mass of the parent peak is different (ie, the side Depending on the presence or absence of the chain and the number of chains, there are several cores having the same mass but different masses), and the existence ratio is proportional to the presence ratio of the parent.

iv. Thus, in the group of “no hetero atom, DBE value = 10”, there are a large number of cores that differ depending on what the parent is derived from.
Then, as shown in FIG. 12, these many cores are arranged in order from the smallest parent mass to the largest based on the parent mass from which they are derived.

v. Cores containing heteroatoms form separate “classes” for each type and number of heteroatoms and are performed as described above.
As described above, all the cores are grouped into “classes” for each of the same “type and number of heteroatoms and DBE value”, and arranged according to the order of the parent mass from which each core belonging to the class is derived. I have created something.

(A-2) “Work to allocate structure”
For all “classes” of “type and number of heteroatoms and DBE value” created as described above, structures are assigned to all the cores existing in the set.
Hereinafter, the class of “no hetero atom. DBE value = 10” will be described.
i. A structure is assigned to each of all the cores existing in the “class” of “no hetero atom. DBE value = 10”. The source of the “assigned structure” is the core structure specified in Step 3. is there.
That is, in Step 3, since the assigned core structure, molecular weight, heteroatom type and number, and DBE value are specified for all peaks after CID, a certain “heteroatom type and number and DBE” are specified. In the “class” of “value”, the core of the peak having the same “type and number of heteroatoms and DBE value” among all peaks after CID is assigned. Therefore, since the condition is only that these values match, there may be a plurality of corresponding peaks. In that case, a plurality of structures having different molecular weights are assigned to one “class”.

  ii. The core having “no hetero atom. DBE value = 10” specified in Step 3 is applied to all the cores existing in the set of “no hetero atom. DBE value = 10”. In Step 3, only the following core X and core Y having different molecular weights are identified from the core structure list as cores having “no hetero atoms. DBE value = 10”, and the abundance ratio is a peak after CID. From the height ratio, it is assumed that the core X is 30% and the core Y is 70%.

The core existing in the set of “no hetero atom. DBE value = 10” is assigned either of these two types as a structure.

iii. How to assign the core X and the core Y to each core existing in the group of “no hetero atom, DBE value = 10” is performed as follows.
In the "preparation", based on the mass of the parent from which the parent was derived, prepared in order from the smallest mass to the largest, in this arrangement, as shown in FIG. 13, the ratio of the core X and the core Y, The line is drawn at 30:70, and the core X is assigned to the small mass side, and the core Y is assigned to the large mass side.
As described above, the structure is assigned to all the cores existing in the group of “no hetero atom. DBE value = 10”.

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

(B) “Work to determine side chains and crosslinks and assign them to core species”
Subsequently, side chains and bridges are determined and assigned to the core by the following procedures i and ii.
Here, “assigning to a core” does not mean to include the determination of which position of which core has a side chain or a bridge.
i. In the above, the structure of the core portion of the single core or the double core and the abundance ratio thereof could be specified, but the side chain bonded to the core and the bridge connecting the cores to each other are still I have not decided.
By the way, if only the core portion is assumed, the molecular weight does not match the value of m / z in the peak obtained by FT-ICR-mass spectrometry. That is, even if the masses based on carbon, hydrogen, and heteroatoms involved in the formation of the core are summed, there is a difference from the m / z value in the peak obtained by FT-ICR-mass spectrometry.
Therefore, the difference is considered to be due to the existence of the side chain bonded to the core and the bridge connecting the cores to each other, and the numbers of carbon and hydrogen are calculated so that the difference is eliminated. Assign to the core as chains and bridges.
For example, it is assumed that the structure of the core portion composed of “core 1-core 2” is assigned to a certain peak of m / z = n by the above procedure. At this time,
Difference (d) = n− (mass of core 1 + mass of core 2)
Is derived from the presence of side chains and crosslinks.

ii. In the above i, the number of carbons and hydrogens to be assigned as side chains and bridges can be obtained, but the structure of side chains and bridges has not been determined yet.
Therefore, in estimating what type of side chains and bridges correspond, for example, the following rules are decided in consideration of the existence probability of combinations of assumed side chains and bridges. It may be estimated.
Rule 1: For a mass difference (d) up to a certain value X, there is no side chain and it is derived only from crosslinking.
Rule 2: Mass difference (d) exceeding a certain value X is assigned to a side chain after assigning a bridge in Rule 1. Rules are also set for the maximum number of carbon atoms that can be taken per side chain, and allocation is made accordingly.

  (C) In this way, the core structure is determined for all the core species whose existence mode is estimated in Step 4, and the side chain and the bridge are further determined.

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

Next, the Example at the time of performing the separation according to type with respect to a multicomponent mixture is described.
I. Fractionation by type Vacuum residual oil (VR) obtained by distillation under reduced pressure of atmospheric residual oil was used as a sample. The vacuum residue (VR) corresponds to heavy oil. Saturated matter (Sa), 1-ring aromatic content (1A), 2-ring aromatic content (2A) obtained by performing a pretreatment method (first and second steps) on the vacuum residue (VR), About each fraction of 3 or more ring aromatics (3A +), polar resin (Po) and polycyclic aromatic resin (PA), and asphaltene (As) separated from marten in the first step Each yield was determined.

In addition, the 1st-2nd process of the pre-processing method was performed with the following method.
<First step: Separation of marten content>
7 g of a sample was weighed into a 500 ml Erlenmeyer flask, 220 ml of n-heptane was added, an air cooling tube was attached, and the mixture was boiled under reflux for 1 hour in an n-heptane insoluble fraction tester.
After boiling at reflux, the mixture was allowed to cool, and the asphaltene content was separated using filter paper to obtain a fraction containing the marten content.

<Second Step: Separation of Marten by Column Chromatography>
The marten content obtained in the first step was separated by column chromatography under the following conditions.
(1) Column conditions for column chromatography Column: 15 mm × 600 mm (gel packed part, glass)
Gel: 40 g of silica gel + 50 g of alumina gel (after activation)
Silica gel: manufactured by Fuji Silysia, Chromato Gel Grade 923AR
Alumina gel: MP Biomebica Ls, 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 (Marten)

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

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

II. Molecular structure identification (1) Step 1
The sample is subjected to mass spectrometry using an FT-ICR-mass spectrometer, and the molecular formula of the molecule belonging to each peak is specified for all the peaks obtained, and 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.
Sample used: Polycyclic aromatic resin (PA) obtained by the above fractionation by type.
Sample preparation method: Dissolve several tens of milligrams of the sample in chloroform, drop about 1 μl on a MALDI (matrix-assisted laser desorption / ionization) plate, and use it as a measurement sample after evaporating the solvent.
Ionization method: Laser desorption ionization method (LDI method) (shot number: 2000, oscillation frequency: 1000 Hz, power: 23%).
As a result of the measurement, a mass spectrum shown in FIG. 14 was obtained.

(A) The specified molecular formula and abundance (expressed in mole fraction) for each peak of the mass spectrum are as 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 assigned in order from the peak with the smallest m / z value.

(2) Step 2
By performing collision induced dissociation (CID) on the sample, the crosslinks and side chains were cleaved for each component constituting the sample.
Details are as follows.
A sample was prepared and ionized by the same method as in Step 1 above.
As a collision induction condition, the collision energy was 30 eV.
The obtained mass spectrum after CID is shown in FIG.

(3) Step 3
About each fragment ion produced | generated by CID of step 2, FT-ICR-mass analysis was performed and the structure and existing ratio of the core which comprises each fragment ion were specified.
For each peak of the mass spectrum after the CID, each core structure and abundance ratio were specified by collating the molecular weight, molecular formula, and DBE value of the core stored in the core structure list prepared in advance.
A part of the core structure list used is shown below.

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

(4) Step 4
The molecules assigned to all the peaks in step 1 are classified 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 the existence ratio were estimated.
Since step 4 is a process processed by the computer, the result cannot be extracted midway.

(5) Step 5
For each molecule whose presence was estimated in step 4, the structure of the core constituting the molecule was determined, and side chains and bridges were further determined and assigned.
Since step 5 is a process processed by the computer, the result cannot be extracted midway.

(6) Step 6
<Identification of molecular structure for sample mass spectrum>
The number of peaks obtained in Step 1 is 3030, but a plurality of molecules having the same molecular formula belong to one peak, that is, a peak having a certain molecular formula. In this example, the molecules displayed by 38,964 JACDs having different structures were specified for the above 3030 molecular formulas.
A part of the results (peak numbers 4 to 3028 are omitted) is 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 is “C ₂₁ H ₁₉ N” as a molecular formula, and this molecular formula indicates that molecules having different structures represented by four types of JACD were assigned.
(A) Of the four types of molecules of the molecular formula “C ₂₁ H ₁₉ N”, for example, “molecular species number 1” will be described. The structure of this molecule is represented by JACD using alphanumeric characters.

(C) In the above table, in order to convert the JACD display using alphanumeric characters into the structure of the core, the bridge and the side chain, a code table for re-reading the alphanumeric information into the structure information may be prepared. For example, the following table.

(D) Using this table, the molecular structure of “molecular species number 1” of the molecular formula “C ₂₁ H ₁₉ N” is as follows.
i. The core 1 is “002007” and has the following structure.

ii. Since the core 2 is “004000”, it has the following structure.

iii. Since bridge 1 is “0BC003”, it has the following structure.

iv. All side chains are “000000”, meaning that they do not exist.
v. In this way, the structure of the molecule of “molecular species number 1” of the molecular formula “C ₂₁ H ₁₉ N” could be displayed and identified by JACD.
(F) Similarly, the structure of all the molecules could be displayed and specified by JACD.

III. Integration of data of each fraction
(1) Saturated content (Sa), 1-ring aromatic content (1A), 2-ring aromatic content (2A), 3 or more aromatic content (3A +), polar resin content (Po) and asphaltene content (As) For the above, the molecular structure was specified in the same manner as in the above polycyclic aromatic resin except that the following was changed.
(A) For the ionization method of saturated, one-ring aromatic, two-ring aromatic, three or more aromatics, and polar resin, atmospheric pressure photoionization (APPI method) (sample flow rate 200 μL / h, The ion accumulation time was 0.2 sec., And the number of integration was 100).
(I) Asphaltene ionization was performed by laser desorption ionization (LDI method) (shot number: 5000, oscillation frequency: 1000 Hz, power: 17%).

(2) Integration of all fractions: saturated (Sa), 1-ring aromatic (1A), 2-ring aromatic (2A), 3 or more aromatics (3A +), polar resin ( Po), polycyclic aromatic resin (PA) and asphaltene content (As), according to the respective yields (abundance ratios) obtained above, the molecular structures and the abundance ratios of all components for all fractions Integrated.

(3) From the above, regarding the vacuum residue (VR) as a sample, the molecular structure and the existence ratio of all molecules constituting the vacuum residue (VR) could be specified.

<Acquisition of melting point and Hansen solubility index value HSP value (δt) of each component of multi-component mixture>
In estimating the property of the model heavy oil, first, the fraction, melting point and HSP value (δt) of each component constituting the model heavy oil are obtained from Comcat based on the JACD of each component specified above.

  In the present embodiment, as a multicomponent mixture, a model heavy oil containing the following 11 types of components (molecular species O-01 to O-11) is used, and the properties (dissolution, aggregation and An example in which the precipitation property is estimated by a computer will be described.

  Table 8 shows the molecular composition (fraction) of the model heavy oil, 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.
Hereinafter, an example of calculating the HSP value (δt) and the melting point by the atomic group contribution method will be described.

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

  Examples of atomic group contribution methods include D.I. W. van Krevelen, K.M. And methods of Krevelen & Hoftyzer according to te Nijenhuis al., "Properties of Polymers (4ed.2009)", Emmanuel Stefanis, of Stefanis & Panayiotou according to Costas Panayiotou al., "Prediction of Hansen Solubility Parameters with a New Group-Contribution Method" A method or the like can be used.

About these, the program estimated from a molecular structure can also be utilized. An example of such a program is HSPiP (http://www.hansen-solubility.Com/).
Furthermore, values obtained by appropriately modifying the values obtained by these various methods can be used.

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

The outline 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 equation.

FIG. 16 shows a schematic diagram of the HSP value. The HSP value is an index of solubility indicating how much a certain substance is dissolved in a solvent, and the solubility is expressed by [dispersion term (δ _d ), polarization term (δ _p ), hydrogen bond term (δ _h )]. It is expressed as a vector.

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

In the formula, the Fd value ((MJ / m ³ ) ^1/2 · mol ⁻¹ ) is a molar attractive 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 attractive constant of each group (atomic group) resulting from the force between dipoles, and Eh value (J · mol ⁻¹ ) is the value of each group (atomic group). Hydrogen bond energy.

V is a molar volume (cm ³ · mol ⁻¹ ), and can be obtained by the following equation (3) proposed by Rheineck and Lin.
In the formula, Vc is the molar volume of each group (atomic group).
D. W. van Krevelen, K.M. According to the literature of “Properties of Polymers (4ed. 2009)” by te Nijenhuis, the Fd value, Fp value, Eh value, and Vc value are shown for many groups. For those groups, the values can be used. (D. W. van Krevelen, K.te Nijenhuis, “Properties of Polymers (4ed. 2009)” pages 195-197 and 215). For groups whose values are not described, values estimated using information on other groups that are structurally approximate 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 group consists of 2 “CH ₃ —” and 28 “—CH ₂ —”. According to the above-mentioned Krevelen & Hoftizer, the Fd value of “CH _3- ” is 420 and the Vc value is 33.5, the Fd value of “-CH _2- ” is 270, and the Vc value is 16 .1 is used, and from these formulas (3) and (2), δd of “O-01” is {(420 × 2) + (270 × 28)} / { (33.5 × 2) + (16.1 × 28)} = 16.22. δp and δh can be calculated in the same manner, and the HSP value (δt) = 16.22.

  In the case of “O-02” to “O-11” molecules, the same calculation is performed. Regarding the group forming the molecule, for the group described in the Krevelen & Hoftizer document, the described values of the Fd value, Fp value, Eh value, and Vc value may be used. For groups not described, values estimated using information on other groups that are structurally approximate may be used.

ii. Calculation of Melting Point Estimation of melting point is one of atomic group contribution methods, and is described in “Jackack, KG, Reid, RC, Chem. Eng. Comm., 57, 233 (1987)”. The described Joback method may be used. That is, the molecular species are decomposed into “groups” forming the molecular structure, and the melting point of the molecular species is calculated from the unique parameter value of each group. Even when using the “average molecular structure”, the melting point of the “fraction (fraction) fractionated based on a specific physical or chemical property” using the group contribution method based on the structure. Is calculated.

(7) Step 7 (Separation into liquid phase component and non-liquid phase component) (S7 in FIG. 1)
Next, a component having a melting point lower than a desired temperature among components constituting the multi-component mixture is classified as a liquid phase component, and a component having a melting point equal to or higher than the desired temperature is classified as a non-liquid phase component.
For example, in the case of the model heavy oil, when 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 "to" O-08 "and" O-11 "molecules having melting points higher than 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 the 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 difference in HSP value between the 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 of the 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 liquidated from the non-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, when RED represented by RED = Δδ / R ₀ is RED <0.3, it is determined as a liquid phase component. Here, R ₀ is a constant for each component in the non-liquid phase component, and RED was calculated with R ₀ = 5 in the model heavy oil.
In addition, 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 the average HSP value of the entire liquid phase after update) (S11 in FIG. 1)
Next, for the HSP value of each component in the updated liquid phase component, a weighted average value weighted by the volume fraction in the updated liquid phase of each component is calculated as the average HSP value of the entire updated liquid phase. To do.

(12) Step 12 (Repeat Steps 9 to 11) (S12 in FIG. 1)
Then, Steps 9 to 11 are repeated until the final stage in which the non-liquid phase component reclassified as the liquid phase component in Step 10 is eliminated.
In this way, the updated liquid phase component at the final stage is used as the liquid phase component at the temperature of the model heavy oil, and the updated average HSP value at the final stage is set as the temperature of the model heavy oil. Determined as the average HSP value of the entire liquid phase. Moreover, the sum total of the fraction of each classified component in the liquid phase component after the update in the final stage is calculated as the liquid phase fraction.

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

(14) Step 14 (classification of non-liquid phase components based on the degree of aggregation) (S14 in FIG. 1)
Next, each component in the non-liquid phase component after the update in the final stage is classified into an aggregated 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 sum of the fractions of each component classified as the aggregate phase component is calculated as the aggregate phase fraction, and the sum of the fractions of each component classified as the solid phase component is calculated as the solid phase fraction. Further, a value obtained by dividing the sum of the aggregation degree of each component classified as the aggregation phase component by the number of the components is calculated as the average aggregation degree of the entire aggregation phase.

For this model heavy oil, first, calculate and estimate the amount and composition of the liquid phase, aggregated phase and solid phase in the absence of solvent, and the degree of aggregation D of each molecule in the aggregated phase and the average aggregated degree of the aggregated phase. did. Experiments were performed from -50 ° C to 350 ° C at 100 ° C intervals.
Table 9 shows in which phase each molecule is present at each temperature. This also indicates the molecular composition of each phase.

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

  As shown in Table 9 and FIG. 17, in the case of no solvent, all are solid phase up to 150 ° C., all become agglomerated phase or liquid phase at 250 ° C. or higher, and the proportion of the liquid phase increases at 350 ° C. The average degree of aggregation of the aggregate phase is 1.53 and 1.25 at 250 ° C. and 300 ° C., respectively.

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

  Thus, 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 aggregation degree of each component in the aggregated phase, and the average aggregation degree of the aggregated phase Based on the above, the solution can be processed by dissolving all or a part of the aggregated phase and the solid phase, or taking measures to suppress aggregation or precipitation of the components.

I. Aggregation Relaxation Treatment First, as an example of treatment, a treatment for dissolving the aggregation phase and the solid phase in the solution, or suppressing aggregation or precipitation of components will be described. Once the amount and composition of each of the liquid phase, the aggregate phase and the solid phase in the solution, the aggregation degree of each component in the aggregate phase and the average aggregation degree of the aggregate phase are known, all or part of the aggregate phase and solid phase can be determined. It is possible to obtain guidelines on what measures should be taken 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 a 30% by mass toluene solution. Table 10 below shows in which phase each molecule is present at each temperature. This also indicates the molecular composition of each phase.

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

  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 dispersed in the solvent in the aggregated phase. At 50 ° C., 100% becomes an agglomerated phase, and above 150 ° C., the agglomerated phase decreases and the liquid phase increases as the temperature rises. It can be seen that the average agglomeration degree of the agglomerated phase decreases with increasing temperature from 1.81 at -50 ° C to 1.27 at 350 ° C.

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

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

Thus, depending on the amount of precipitation of the agglomerated phase and solid phase in the model heavy oil, the precipitation properties, etc.
There are various measures that can be taken. Specifically, for example, the same solvent as in the current situation may be added, another type of solvent (solvent) may be newly added, or the temperature of the solution may be increased. In particular, regarding the addition of the solvent (solvent), any property can be obtained by predicting the properties after the addition of the solvent (solvent) based on the HSP values of the current solution, the solvent to be added (solvent), the aggregation phase, and the solid phase. It is possible to determine what amount of solvent (solvent) having an HSP value should be added.

II. Precipitation promotion process Next, the process for the precipitation promotion in a solution is demonstrated as a process example.
Once the amount and composition of each of the liquid phase, aggregated phase, and solid phase in the solution, the degree of aggregation of each component in the aggregated phase, and the average aggregate degree of the aggregated phase are known, the estimated liquid phase, aggregated phase in the solution And guidance on what measures should be taken to precipitate one or more components based on the amount and composition of each of the solid phases and the degree of aggregation of each component in the aggregated phase and the average aggregation degree of the aggregated phase. Can be obtained.

  As described above, there are various measures that can be taken depending on the properties of the liquid phase in the solution. Specifically, for example, a new solvent (solvent) may be newly added, or the temperature of the solution may be lowered. It is done. In particular, regarding the addition of the solvent (solvent), any property can be obtained by predicting the properties after the addition of the solvent (solvent) based on the HSP values of the current solution, the solvent to be added (solvent), the aggregation phase, and the solid phase. It is possible to determine what amount of solvent (solvent) having an HSP value should be added.

  Thus, regarding the liquid phase, the aggregated phase, and the solid phase in the solution, the amount and composition thereof can be calculated and estimated, and the aggregation degree of each component in the aggregated phase and the average aggregation degree of the aggregated phase can be calculated. Therefore, for example, if appropriate measures such as selecting a 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 are removed. It becomes possible to dissolve or suppress aggregation or precipitation of components, or to deposit one or more components.

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

<Property estimation device for multi-component mixture>
Next, with reference to FIG. 20, an embodiment of the property estimation apparatus for a multicomponent mixture of the present invention will be described. FIG. 20 is a functional block diagram of the multi-component mixture property estimation apparatus according to the embodiment. By causing the computer to execute the program of the present invention, the computer functions as a property estimation device for a multi-component mixture.
In FIG. 20, an interface for inputting and outputting information is omitted.

  The apparatus includes an arithmetic device 1 and a storage unit 2. The arithmetic device 1 may be composed of one CPU, or may be composed of a plurality of arithmetic devices connected to each other via a communication line. Further, 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.

  The computing device 1 includes a component information acquisition unit 10, an initial classification unit 20, a liquid phase calculation unit 30, and a non-liquid phase calculation unit 40.

I. Component information acquisition part The component information acquisition part 10 acquires the fraction, melting | fusing point, and HSP value about each component which comprises the multicomponent mixture made into object. Information on these components may be obtained from the storage unit 2 in which information about the multi-component mixture is stored as a database.

  When the information on these components is not stored in the database, the component information calculation unit 11 may estimate the necessary parameters for each component.

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

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

Alternatively, as described above, the “component” is classified as “a mass of a solution bundled with a specific physical or chemical property”, in other words, “fractionation based on a specific physical or chemical property. When used in the sense of “fractionated fraction (fraction)”, this “method based on information on molecular composition (molecular structure)” can be applied as follows.
That is, for each of “fractions (fractions) fractionated based on a specific physical or chemical property”, NMR, elemental analysis, mass spectrum, etc. are measured, and a known method is used. The “average molecular structure” of the fraction (fraction) can be obtained. If the “average molecular structure” thus obtained is used, 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 acquired from Comcat. This process is performed by a computer.

  (3) Moreover, based on JACD of each molecular species, HSP value data of each molecular species is acquired from Comcat. This process is performed by a computer.

(II. Initial classification part)
The initial classifying unit 20 classifies a component having a melting point lower than a desired temperature among components constituting the multi-component mixture as a liquid phase component, and classifies a component having a melting point higher than a desired temperature as a non-liquid phase component. To do. That is, the amount and composition of the “liquid phase” at a certain temperature above the melting point of the solvent is determined. A component having a melting point lower than that temperature is a component present 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 the 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 component by the fraction of each component in the liquid phase, preferably by the volume fraction. is there.

  The HSP value difference (Δδ) calculation unit 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 component.

The reclassifying 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 reclassifies each component reclassified as the liquid phase component. The liquid phase component and the non-liquid phase component are updated by incorporating the phase component into the liquid phase component.
If there is a component to be dissolved, the reclassifying unit 33 adds it to the liquid phase and recalculates the HSP value of the entire liquid phase.

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

  Then, the update of the average HSP value, the liquid phase component, and the non-liquid phase component (aggregated phase, solid phase) is repeated until the final stage in which the non-liquid phase component reclassified as the liquid phase component disappears.

  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 includes an aggregation degree calculation unit 41, an aggregation phase, a solid phase classification unit 42, an aggregation phase information calculation unit 43, and a solid phase information calculation unit 44 in order to estimate the properties of the non-liquid phase. . The non-liquid phase calculation unit 40 determines, for example, the amount of agglomerated phase, the components, the agglomeration degree of each agglomerated component, the average agglomeration degree of the agglomerated phase, and the amount and composition of the solid phase as the non-liquid phase properties. .

  The aggregation degree calculation unit 41 calculates the aggregation degree of each component in the non-liquid phase component after update at the final stage at a desired temperature, 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 component updated in the final stage. Specifically, classification is performed as follows.

  For each component in the non-liquid phase component that has not finally dissolved in the liquid phase, the degree of aggregation is determined based on the HSP value and the HSP value of the entire liquid phase. The agglomeration degree D of each of the agglomerated components is calculated by the functional equation (A) using the HSP value of the liquid phase, the HSP value of the agglomerated component, the concentration of the agglomerated component, and the temperature of the field as variables. can do.

D (p, q) = M _AS (K ₀ + K ₁ p + K ₂ q + K ₃ p ² + K ₄ pq + K ₅ q ² + K ₆ p ³ + K ₇ p ² q + K ₈ pq ² + K ₉ q ³ ) (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
It is represented by

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

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

  q is represented by q = logC, and C is the concentration of the component in the non-liquid phase component aggregated.

M _AS is a constant determined by the component type. For example, when the aggregated phase component and the solid phase component of the multi-component mixture are asphaltenes, M _AS is as follows. Canadian oil sand asphaltene (CaAs): 1.319, Middle East asphaltene 1 (ArAs1): 1.000, Middle East asphaltene 2 (ArAs2): 1.136.

K _{0 to} K ₉ are coefficients obtained empirically and have the following constant values.
K ₀ = −1.26929,
K ₁ = 9.42231,
K ₂ = 0.363439,
K ₃ = −11.1925,
K ₄ = 0.093622,
K ₅ = −0.15436,
K ₆ = 5.333743,
K ₇ = −0.20868,
K ₈ = 0.077223,
K ₉ = 0.019492
It is.

As described 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.
In addition, the values such as L ₀ , L _1, L _2, M _AS, and K _{0 to} K ₉ indicated by numerical values in the above can take various numerical values depending on the object, and are limited to the above numerical values. is not.

  The agglomerated phase / solid phase classification unit 42 classifies a component having an aggregation degree less than a predetermined threshold among the non-liquid phase components after the update in the final stage as an aggregation phase component, and a component having an aggregation degree equal to or higher than the predetermined threshold Are classified as solid phase components. That is, a component having an aggregation level at the aggregation level is defined as an aggregation phase component, and a component at the precipitation level is defined as a 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 the aggregated particles. It is considered that the particle size is submicron or more and cannot be dispersed in the liquid and is precipitated. When the degree of aggregation is D ≧ 5, it can be generally determined that the component species are precipitated, but this threshold value 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 relative to the entire solution) as the aggregated phase fraction. Further, the aggregated phase information calculation unit 43 calculates a value obtained by dividing the sum of the aggregation degrees of each component classified as the aggregated phase component by the number of the components as the average aggregation degree of the entire aggregated phase.

  The solid phase information calculation unit 44 calculates the total amount of each component classified as a solid phase component (a fraction relative 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 for estimating the molecular structure using JACD, associating the estimated molecular structure information with the physical property values, and estimating the properties of the multi-component mixture using the aggregation model are performed by hardware or software. Or a combination of these. When executing processing by software, install the program that records the processing sequence in the memory in the computer built in the dedicated hardware, or install it on a general-purpose computer that can execute various processing Can be executed.

  For example, the program can be recorded in advance on a hard disk or ROM as a recording medium. The program can be stored (recorded) temporarily or permanently in a removable recording medium such as a flexible disk, CD-ROM, MO disk, DVD, magnetic disk, or semiconductor memory.

  In addition to installing the program from the removable recording medium as described above, the program can 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, the program transferred in this way can be received and installed in a recording medium such as a built-in hard disk.

  In addition, the various processes described in this specification are not only executed in time series according to the description, but may be executed in parallel or individually according to the processing capability of the apparatus that executes the processes and as necessary. . Further, in this specification, the system is a logical set configuration of a plurality of devices, and is not limited to a device in which each device is in the same casing.

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

  According to the present invention, since the structure of the molecules constituting petroleum can be specified, it can be widely applied in analyzing 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 the petroleum refining facility.

Claims (28)

A method for estimating the properties of a multi-component mixture by a computer,
(1) performing mass spectrometry on the multi-component mixture, for each of the obtained peaks, identifying the molecular formula of the molecule belonging to the peak, and further identifying the abundance ratio of the molecule;
(5) For each molecule whose molecular formula is specified in step (1), determining the structure of the core constituting the molecule, and further determining and assigning side chains and bridges;
(6) obtaining a melting point and a Hansen solubility index value of each component from the molecular structure of each component of the multicomponent mixture identified in the steps (1) and (5);
(7) Of each component constituting the multi-component mixture, a component having a melting point lower than a desired temperature is classified as a liquid phase component, and a component having a melting point higher than the desired temperature is classified as a non-liquid phase component. Steps,
(8) calculating an 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 a fraction in the liquid phase of each component; ,
(9) calculating the difference between the average Hansen solubility index value of the entire liquid phase and the Hansen solubility index value of each component in the non-liquid phase component;
(10) Based on the difference, each component in the non-liquid phase component is reclassified as a liquid phase component or a non-liquid phase component, and each component reclassified as a liquid phase component is converted from the non-liquid phase component to the liquid phase component. And renewing the liquid phase component and the non-liquid phase component;
(11) The average Hansen solubility index value of the entire updated liquid phase is calculated as a weighted average value obtained by weighting the Hansen solubility index value of each component in the updated liquid phase component by the fraction of each component in the liquid phase. Steps,
(12) repeating the steps (9) to (11) until a final stage in which the non-liquid phase component reclassified as the liquid phase component in the step (10) is eliminated.
A method for estimating the properties of a multi-component mixture.   The method of claim 1, further comprising a step (2) of performing a collision induced dissociation on the multi-component mixture after the step (1).   After the step (2), mass analysis is performed on each fragment ion generated by the collision-induced dissociation in the step (2), and the structure and the existence ratio of the core constituting each fragment ion are specified (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 the “type and number of heteroatoms and the DBE value”, and are assigned to the respective “classes”. The method according to claim 3, further comprising the step (4) of estimating the existence mode and the existence ratio of all the molecules to which the molecule belongs.   In specifying the structure of each core in the step (3), information on the core after the collision-induced dissociation obtained in the step (2) and information on the core described in the core structure list prepared in advance are included. The method according to claim 3 or 4, wherein collation is performed to identify the structure of each core.   The method according to claim 5, wherein the core structure list is a list of various cores that can be assumed to constitute each component constituting the multi-component mixture.   The molecular structure of each component constituting the multi-component mixture is represented by the type of attribute including a core, a side chain, and a bridge, and the number of attributes, according to any one of claims 1 to 6. The method described.   In the step (4), when the molecule belonging to the class is multi-core, the number of hetero atoms of the same type existing in the plurality of cores constituting the multi-core The cores are combined so that the sum of the DBE values of the plurality of cores matches the type and number of heteroatoms of the class and the DBE value. The method according to one item.   In the step (4), “the existence ratio” is a product of the existence ratio of each of a plurality of cores constituting the multicore when the molecule belonging to the class is a multicore. 9. A method according to any one of claims 4 to 8, characterized in that it is.   The said multi-component mixture is one fraction obtained by fractionating a certain multi-component mixture into two or more arbitrary parts, The any one of Claims 1-9 characterized by the above-mentioned. the method of. A method for determining a composition model of a multi-component mixture using a computer,
Fractionating the multicomponent mixture into two or more arbitrary portions; and
For each fraction fractionated in the step A, the method according to any one of claims 1 to 10, wherein the molecular structure and the existing ratio of each component constituting each fraction are specified, and And C, which integrates the molecular structure and abundance of all components obtained for all fractions according to the mixing ratio of each fraction fractionated in step A.   The method of estimating the physical property value of a multicomponent mixture based on the molecular structure of each component which comprises the multicomponent mixture, and its abundance ratio specified by the method in any one of Claims 1-10.   13. The method according to claim 1, further comprising a step of calculating a sum of the fractions of each component in the liquid phase component after the update in the step (12) as a liquid phase fraction. The method described.   The aggregation degree of each component in the non-liquid phase component updated in the step (12) at the desired temperature, the average Hansen solubility index value of the entire liquid phase after the update in the step (12), and the step Calculating based on the difference between the Hansen solubility index value of each component in the updated non-liquid phase component in (12) and the concentration of each component in the updated non-liquid phase component in the step (12); 14. The method according to any one of claims 1 to 13, further comprising: The method according to claim 1, wherein the degree of aggregation (D) of each component in the non-liquid phase component is calculated by the following formula (A).
D (p, q) = M AS (K 0 + K 1 p + K 2 q + K 3 p 2 + K 4 pq + K 5 q 2 + K 6 p 3 + K 7 p 2 q + K 8 pq 2 + K ₉ q ³ ) (A)
(Where
p is p = (L ₀ (T −25) + L ₁ ) RED _g when the desired temperature T is T ≦ 150 ° C., and the desired temperature T is 150 ° C. <T ≦ 200 ° C. When 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
L ₀ , L ₁ and L ₂ are coefficients,
RED _g, when the _{RED ≧ 0.3, RED g = RED} , when the RED _<0.3, expressed as RED g = 0.3,
RED is represented by RED = Δδ / R ₀ ,
Δδ is the difference between the average Hansen solubility index value of the entire liquid phase and the Hansen solubility index value of each component in the non-liquid phase component,
R ₀ is a constant of each component in the non-liquid phase component,
q is represented by q = logC,
C is the concentration of each component in the non-liquid phase component,
M _AS and K _{0 to} K ₉ are coefficients. )   Among the components in the non-liquid phase component after the update in the step (12), the component having the aggregation degree less than a predetermined threshold is classified as an aggregation phase component, and the component having the aggregation degree equal to or higher than the predetermined threshold. The method according to claim 1, further comprising the step of classifying as a solid phase component. Calculating the sum of the fractions of each component classified as the aggregate phase component as an aggregate phase fraction;
The method according to claim 1, further comprising a step of calculating a total of the fractions of each component classified as the solid phase component as a solid phase fraction.   The method further comprises a step of calculating an average aggregation degree of the entire aggregate phase as a value obtained by dividing the sum of the aggregation degrees of each component classified as the aggregate phase component by the number of the components. 18. The method according to any one of items 17.   The method according to claim 1, wherein the multi-component mixture is petroleum.   The method according to claim 1, wherein a desired type of solvent is mixed in the multi-component mixture in a desired fraction.   21. A method according to any one of the preceding claims, characterized in that the multi-component mixture is heavy oil or a mixture of heavy oil and solvent. By the method according to any one of claims 1 to 21, the property of the raw multi-component mixture is estimated, and further based on the property estimation result,
When a desired type of solvent is mixed with the raw multicomponent mixture in a desired fraction,
When the temperature of the raw multi-component mixture is changed to a desired temperature, or a desired type of solvent is mixed with the raw multi-component mixture in a desired fraction and the temperature of the raw multi-component mixture is changed to a desired temperature. Predict the properties of the new multi-component mixture
Based on the prediction, the desired type of solvent is mixed into the raw multi-component mixture in the desired fraction, or the temperature of the raw multi-component mixture is changed to the desired temperature, or the desired Mixing different types of solvents into the raw multi-component mixture in the desired fraction and changing the temperature of the raw multi-component mixture to the desired temperature;
A method for treating a multi-component mixture.   The desired type of solvent and the desired fraction, and / or the desired temperature is determined by the predicted properties of the new multi-component mixture, the aggregated phase component and the solid phase component in the original multi-component mixture estimated. A solvent and a fraction and / or a temperature at which all or a part of the solvent is dissolved or the aggregation or precipitation of the aggregation phase component and the solid phase component is suppressed. A process for treating the multi-component mixture as described.   The desired type of solvent and the desired fraction, and / or the desired temperature may be determined from the non-solid phase components in the original multi-component mixture where the predicted properties of the new multi-component mixture are estimated. 24. The method for treating a multi-component mixture according to claim 22 or 23, wherein the solvent and the fraction and / or the temperature are such that one or more kinds of components are deposited. A device for estimating properties of a multi-component mixture,
A component information acquisition unit for acquiring a fraction of each component constituting the multi-component mixture, a melting point, and a Hansen solubility index value;
An initial classifying unit that classifies a component having a melting point lower than a desired temperature among components constituting the multi-component mixture as a liquid phase component, and classifies a component having a melting point equal to or higher than the desired temperature as a non-liquid phase component. When,
A liquid phase calculation unit for estimating the properties of the liquid phase,
The component information acquisition unit
Composition of each component of the multi-component mixture obtained by mass spectrometry of the multi-component mixture and composition information of the fraction, physical property information of melting point and Hansen solubility index value of each component linked to the component information, Get
The liquid phase calculation unit is
As a weighted average value obtained by weighting the Hansen solubility index value of each component classified as the liquid phase component by the fraction in the liquid phase of each component, the average Hansen solubility index value of the entire liquid phase is calculated,
Calculate the difference between the average Hansen solubility index value of the entire liquid phase and the Hansen solubility index value of each component in the non-liquid phase component,
Reclassify each component in the non-liquid phase component as a liquid phase component or a non-liquid phase component based on the difference, and incorporate each component reclassified as a liquid phase component from the non-liquid phase component to the liquid phase component. Update the liquid phase component and the non-liquid phase component,
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 fraction in the liquid phase of each component, the average Hansen solubility index value of the entire liquid phase after the update is calculated,
Repeat the update of the average Hansen Solubility Index value, liquid phase component, and non-liquid phase component until the final stage when there are no non-liquid phase components reclassified as liquid phase components
A device for estimating properties of a multi-component mixture. A non-liquid phase calculation unit for estimating a non-liquid phase property;
The non-liquid phase calculation unit calculates the aggregation degree of each component in the updated non-liquid phase component at the final stage at the desired temperature, the average Hansen solubility index value of the entire liquid phase, and the non-liquid phase component. The property of the multi-component mixture according to claim 25, wherein the property 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 updated in the final stage. Estimating device.   The operation method of the apparatus regarding the multicomponent mixture characterized by setting operation conditions based on the physical property value of the multicomponent mixture estimated by the method as described in any one of Claims 1-21.   27. A computer program for executing the method according to any one of claims 1-21, 22-24 and 27 or the apparatus according to claim 25 or 26.