JP2021162938A - Method for estimating precipitation amount of sediment - Google Patents

Abstract

To provide a novel method for highly accurately estimating a precipitation amount of sediment in a multi-component mixture.SOLUTION: An estimation method of a precipitation amount of sediment in a multi-component mixture by a computer includes: a step (1) of providing a fraction, a melting point and Hansen solubility index value of each component constituting a multi-component mixture on the basis of molecular structure information of each component; a step (2) of estimating a solid phase amount in the multi-component mixture on the basis of the fraction, the melting point and Hansen solubility index value of each component; a step (3) of providing correction factor information in the precipitation amount estimation of sediment by multivariate analysis on the basis of physical property value information of at least one component selected from a precipitation related component, a compatibility related component and an aggregation related component in the multi-component mixture; and a step (4) of matching the precipitation amount of sediment in the multi-component mixture on the basis of the solid phase amount and the correction factor information.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for estimating the amount of sedimentation in a multi-component mixture. More specifically, the amount of sedimentation is determined by combining the estimation information of the solid phase amount of the multi-component mixture and the specific correction factor information using a computer. It relates to a method of estimation, a device, a system, a computer used therein and a method of using the computer, and a computer program and a recording medium thereof for causing the computer to execute the device.

In the operation of various equipment related to petroleum refining, raw material oil is usually analyzed based on the overall physical properties such as specific gravity, viscosity, and distillation properties (boiling point), and the operation results of oil types with similar past data are obtained. The method of determining the operating conditions with reference is taken.
However, with the diversification of imported crude oil types these days, it is not easy to find similar historical data. Furthermore, from the viewpoint of improving driving efficiency and protecting the environment, it is no longer a matter of simply following past driving results.
Therefore, instead of grasping the entire petroleum as a whole, such as specific gravity, viscosity, and distillation properties, we grasp the chemical structure and abundance ratio at the level of the hydrocarbon molecules that make up the petroleum, and obtain it by doing so. It has been considered that if the operating conditions can be set based on the knowledge of the estimated physical property values and the like, more efficient operation based on objectivity can be performed. Therefore, in the petroleum industry, the emergence of technology for grasping petroleum at the molecular level has been awaited.
However, petroleum is a mixture consisting of a huge number of hydrocarbon molecules, and heavy oil in particular has an extremely large number of molecules having a large molecular weight and a complicated chemical structure. Therefore, each of such molecules is present. For each, it was very difficult to identify the chemical structures and their abundance ratios.

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

Further, in the treatment of heavy oil containing a large amount of residual components such as asphalt, it is required to reduce the residual amount as much as possible and improve the utilization rate of crude oil. In the process of petroleum refining, it is necessary to alleviate and suppress the agglutination of asphaltene, which is a precursor of cork, in various situations such as the decomposition treatment of heavy oil. Therefore, it is usual practice to premix a solvent (solvent) that alleviates or suppresses the aggregation of asphaltene with the raw material oil.

However, if the processing amount of heavy oil is increased and the decomposition rate is increased, solid precipitates will accumulate on the equipment inside the heavy oil processing equipment and block the flow path, resulting in unplanned outage of the entire process. If you try to avoid it, you may have to limit the crude oil type or suppress the heavy oil treatment method. For example, a decompression residual oil hydrocracking device is a device that hydrocrackes decompressed residue (VR) to produce high-value-added gasoline and light oil, but equipment blockage due to sediment deposition occurs relatively frequently. It is a constraining factor in operation. Although the reduced-pressure residual oil hydrocracking apparatus is normally operated in two series, fouling occurs and precipitates often occur in the heat exchanger after distillation, which still causes a decrease in productivity. .. Regarding this fouling, in a study by an oil company, it has been found that there is a high correlation between the rate of increase in differential pressure of the heat exchanger, which is an index of this fouling, and the sediment test at 150 ° C.

On the other hand, in Patent Document 3, the applicant reports that there is a certain relationship between the difference (Δδ) in the Hansen solubility index value (HSP value) between asphaltene and the solvent and the degree of cohesion of asphaltene. There is. Further, in Patent Document 4, the molecular structure and abundance ratio of each component are specified by using the difference (Δδ) between the average HSP value of the entire multi-component aggregation model liquid phase and the HSP value of each component in the non-liquid phase component. Applicants have reported a method for estimating the properties of each component in a multi-component mixture based on a multi-component aggregation model (MCAM). MCAM is expected to be established as a tool that can be used to solve various practical problems in the petroleum refining field caused by asphaltene agglutination.

Japanese Patent Publication No. 2014-500506 Japanese Patent Publication No. 2014-503816 Japanese Unexamined Patent Publication No. 2014-218634 Special Table 2020-502495

Under such technical circumstances, the applicant examined the consistency between the measured values of various multi-component mixtures and the estimated values obtained by MCAM, and as a result, the molecular structure and its composition in the multi-component mixture were found. Although it is consistent with the estimated value of MCAM, it was found that the estimated value of the precipitation amount of sediment obtained by MCAM does not match the measured value of the precipitation amount of sediment. Therefore, as a result of further diligent studies, the applicant estimated the amount of sediment precipitation with high accuracy by incorporating a specific correction factor that affects precipitation in the construction of the sediment precipitation prediction model of the multi-component mixture by MCAM. Found to get. The present invention is based on such findings.

Therefore, one object of the present invention is to provide a new method for estimating the amount of sediment precipitation in a multi-component mixture with high accuracy.

In order to achieve the above object, the present inventors have created the following inventions. That is, the gist of the present invention is as follows.
A computer-based method for estimating the amount of sediment deposited in a multi-component mixture.
(1) A step of providing a fraction, melting point and Hansen solubility index value of each component based on the molecular structure information of each component constituting the multi-component mixture.
(2) A step of estimating the solid phase amount in the multi-component mixture based on the fraction, melting point and Hansen solubility index value of each component.
(3) Based on the physical property value information of at least one component selected from the precipitation-related component, the compatibility-related component and the aggregation-related component in the multi-component mixture, the correction factor information in the estimation of the precipitation amount of the sediment is provided by multivariate analysis. It is characterized by including (4) a step of matching the amount of sediment precipitation in the multi-component mixture based on the solid phase amount and the correction factor information.

In another embodiment of the present invention, there is also provided an apparatus for estimating the amount of sedimentation of sediments in a multi-component mixture, a system and a method for operating them, a computer program for executing them, a recording medium thereof, and a computer for storing the same. Will be done.

According to the present invention, by combining the estimation information of the solid phase amount of the multi-component mixture obtained from the multi-component aggregation model using a computer with the specific correction factor information, the amount of sedimentation in the multi-component mixture can be highly accurate. Can be estimated with.

It is a flowchart explaining the method by embodiment of this invention. It is a flowchart explaining step (1) of the method by embodiment of this invention. It is a flowchart explaining step (2) of the method by embodiment of this invention. It is a functional block diagram of the sediment precipitation amount estimation apparatus of the multi-component mixture by embodiment of this invention. It is a flowchart which shows the separation pretreatment method of the reduced pressure residual oil (VR) sample in Test Example 1. FIG. It is a figure which showed the relationship between the measured sedimentation precipitation value and the solid-state amount estimated by MCAM for the sediment of high phasoring and low phasoring. It is a figure which shows the relationship between the measured value of sediment precipitation and the measured value of alfalten (As). It is a figure which shows the relationship between the measured value of sediment precipitation and the measured value of toluene insoluble matter (TI). It is a figure which shows the result of the product oil analysis (component analysis which dissolves a precipitate). It has been shown that aromatics (3 rings or more: 3A ⁺ ) and polar resin (Po) influence the dissolution of the precipitate. It is a figure which shows the relationship between the measured value of sediment precipitation and As / (3A ^{+ + Po).} It is a figure which shows the result of having performed the N class analysis for each division of the DAgg value for each core. It is a figure which shows the relationship between the measured value of sediment precipitation and the fraction (N2 class fraction (double core)) of the aromatic component of two rings containing two nitrogen atoms. It is a figure which shows the relationship between the measured value of sediment precipitation and the fraction (N2 class fraction (single core)) of the aromatic component which contains two nitrogen atoms and has one ring. It is a figure which shows the relationship between the measured sedimentation value and the precipitation prediction formula shown in Equation 2.

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

(2) "Ingredients"
A "component" is a "mass of a mixture bound by a particular physical or chemical property", that is, a "fraction" fractionated based on a particular physical or chemical property. ) ”. Examples of the method of grouping based on specific physical or chemical properties include a method of specifying a boiling point range in a distillation test and fractionating those in that temperature range as one component. In this case, the mixture is an "aggregate of fractions". Alternatively, the "component" may be regarded as an "aggregate of molecules recognized to belong to the same molecular species", which are individual members constituting the multi-component mixture. Here, "identical" means "completely identifying the molecular structure and then being the same", or "isomers having the same molecular structure but different structures). It may be understood as meaning "to be the same", and for example, it may be understood to mean "the same in the structure specified by the method such as JACD" which will be described later. Furthermore, it may be broadly understood to mean "an aggregate of molecules grouped together based on an arbitrarily determined standard".

(3) "Compose"
The phrase "constituting 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, "each constituent component" is appropriately determined according to the degree of detail required to specify the molecular species as a component. do it. For example, only molecular species having a certain abundance (absence ratio) or more in a multi-component mixture may be regarded as "constituent components". It is not always necessary to identify the molecular structure of all of a huge variety of molecular species such as petroleum, and molecular species having only a trace amount may be ignored if necessary. For example, when a polycyclic aromatic resin (PA) is targeted as a "multi-component mixture", the presence of paraffin compounds and olefin compounds as components constituting PA may be ignored.

(4) "Partsper notation"
The "partsper" may be any one indicating the abundance ratio such as mass fraction, volume fraction, mole fraction, etc., and is a concept including any of them. When calculating the average Hansen solubility index value of the entire liquid phase, a volume fraction is preferably used, and it is calculated as a weighted average value weighted by the volume fraction of each component in the liquid phase.

(5) "Specify the molecular structure", "Molecule"
"Specifying a molecular structure" includes any act of specifying some information about the structure of a molecule with respect to the "molecule" in the above "component". The degree and display method may be appropriately selected according to the purpose and necessity. 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 portion may be specified, and the structure of the side chain portion and the crosslinked portion may not be specified and may be left as the molecular formula.
In the present specification, the molecular structure is preferably specified by "JACD" described later. The molecule whose structure is specified by "JACD" is a concept including all isomers due to the difference in the binding position of the attributes described later. In the present specification, the “molecule” may be regarded as a concept including all isomers.

(6) "Specify the abundance ratio of each component"
"Specifying the abundance ratio of each component" includes any act of specifying the abundance ratio of each component constituting the mixture. In addition, it does not mean that the abundance ratio must be specified for all the component species constituting the mixture, including components that are present in an amount that is difficult to detect by analytical techniques and components that do not need to be specified. It is not the case that "the abundance ratio of each component is specified" only after the abundance ratio of all the components is specified. Such trace components and the like may be collectively treated as "other components". Furthermore, these need not be excluded from the range of "each component constituting the mixture" and not included in the denominator for calculating the abundance ratio of other components.

(7) "All"
In the present specification, "all" does not necessarily mean "100% all". For example, the term "all peaks" in the mass spectrum literally means not only "100% all peaks" but also, for example, molecules that are not always necessary for the purpose of study in that situation. Peaks and peaks that are difficult to distinguish may be considered to mean other peaks after being appropriately excluded.

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

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

(10) "Core", "Single core", "Double core"
The "core" is a kind of "attribute" described in the section of "JACD" described later, and specifically, the aromatic ring or the naphthenic ring itself, or the aromatic ring and the naphthenic ring are directly bonded instead of being crosslinked. Heterocycles are directly bonded to aromatic rings or naphthenic rings rather than crosslinked. Since cross-linking or side chains are attributes separate from the core, "core" means one that does not have any cross-linking or side chains.
On the other hand, the "single core" is a concept that refers to a molecule having only one core. Since it is a concept that refers to a molecule, it also includes those with side chains attached to the core. A molecule in which two or more of the cores are crosslinked is called a "multi-core". Since "multi-core" also means a molecule, it also includes those having side chains attached to the core. A molecule formed by cross-linking two cores is called a "double core".
For example, the naphthalene molecule shown below is a "single core" because it is composed of one aromatic ring, and is not a double core composed of two benzene rings.

(11) "DBE value"
The "DBE value", molecular formula, when _{"C c H h N n O o} S s ", is a value calculated by the following equation (1).
DBE = c−h / 2 + n / 2 + 1 ・ ・ ・ (1)
(In the formula, c is the number of carbon atoms, h is the number of hydrogen atoms, n is the number of nitrogen atoms, o is the number of oxygen atoms, and s is the number of sulfur atoms.)
This value generally indicates the degree of unsaturatedness in the molecule, especially the presence of double bonds and rings.

(12) "JACD""Juxtaposited Attributes for Chemical-Structure Description)"
"JACD" is a new display method for molecular structure, which displays the structure of a molecule according to the type of attribute and the number of attributes. It does not show where the attributes are combined in other attributes.
In the above, the "attribute" is a concept that refers to a chemical structural part that constitutes a molecule. In the case of aromatic compounds, it specifically refers to the above-mentioned "core", "crosslink" and "side chain".
According to this labeling method, the structure of each of the huge number of molecules constituting petroleum can be specified to a necessary and sufficient extent.
The molecule represented by the following chemical formula will be described as an example.

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

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

(13) "Physical characteristic value"
The "physical characteristic value" is included in the "physical characteristic value" regardless of the name as long as it expresses the physical or chemical property, property, or property of the substance. In the present specification, the “physical property value” is not limited to these, but is, for example, the melting point, the Hansen solubility index value, the generated Gibbs free energy, the ionization potential, the polarization rate, the dielectric constant, the vapor pressure, and the liquid density. , API degree, gas viscosity, liquid viscosity, surface tension, boiling point, critical temperature, critical pressure, critical volume, heat of formation, heat capacity, dipole moment, enthalpy, entropy and the like.

(14) "Oil"
In the present specification, the term "petroleum" also refers to crude oil, fractions obtained by distilling crude oil, and fractions obtained by subjecting the fractions to treatments such as reforming and decomposition by a secondary device. A generic concept that includes. Alternatively, a fraction obtained by distilling crude oil may be further fractionated into components such as saturated hydrocarbons and aromatic hydrocarbons.

(15) "Petroleum-related equipment"
In the present specification, the "device related to petroleum" includes all devices related to petroleum processing, such as a distillation device, an extraction device, a reformer, a hydrogenation reaction device, a desulfurization device, and other devices involved in a chemical reaction. "Petroleum-related equipment" is also collectively referred to as "petroleum refining equipment."

(16) "Sediment"
In the present specification, "sediment" is a precipitate measured according to the "sediment test" IP-375 method (ISO 10307-1, ASTM D4870), and its mass% is referred to as "sediment precipitation amount". The filtration temperature was 150 ° C.

<Method of estimating the amount of sedimentation in a multi-component mixture>
According to one embodiment of the present invention, as shown in FIG. 1, it is a method of estimating the amount of sediment precipitation in a multi-component mixture by a computer.
(1) A step of providing a fraction, melting point and Hansen solubility index value of each component based on the molecular structure information of each component constituting the multi-component mixture.
(2) A step of estimating the solid phase amount in the multi-component mixture based on the fraction, melting point and Hansen solubility index value of each component.
(3) Based on the physical property value information of at least one component selected from the precipitation-related component, the compatibility-related component and the aggregation-related component in the multi-component mixture, the correction factor information in the estimation of the precipitation amount of the sediment is provided by multivariate analysis. And (4) a method including a step of matching the amount of sediment precipitation in the multi-component mixture based on the solid phase amount and the correction factor information is provided.

Step (1): Based on the molecular structure information of each component constituting the multi-component mixture, the poly is in the present embodiment with reference to the flowchart of step 2 in which the fraction, melting point and Hansen solubility index value of each component are provided. Step (1) for identifying the molecular structure of each component of the component mixture will be described.
Step S1 (mass spectrometry) (S1 in FIG. 2)
The first step is to perform mass spectrometry on the multi-component mixture, specify the molecular formula of the molecule belonging to the peak for each of the obtained peaks, and further specify the abundance ratio of the molecule. That is, it is a step of performing mass spectrometry on a multi-component mixture, identifying the molecular formula of the molecule belonging to each peak for all the peaks obtained by the mass spectrometry, and further specifying the abundance ratio of the molecule corresponding to the molecular formula. ..

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

Step S2 (collision-induced dissociation) (S2 in FIG. 2)
Step S2 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 a molecule is ionized and collided with an inert gas such as argon to crosslink and break a side chain. Usually, it is preferable to apply collision energy so that the crosslinks and side chains in each component constituting the multi-component mixture are cleaved. By cross-linking and breaking the side chains, fragment ions are generated for each core. This core may have an aliphatic group having about 0 to 4 carbon atoms as a side chain, which 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 obtained peak m / z, but information on the "core" of the molecule. Cannot be obtained. Therefore, by further performing collision-induced dissociation to cleave the crosslinks and side chains in each molecule constituting the multi-component mixture, the type of core existing in the entire multi-component mixture can be known.
As conditions for performing 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. In addition, 40 kcal / mol corresponds to 32 eV when the molecular weight is 700.

Step S3 (Specification of structure and abundance ratio of each core) (S3 in FIG. 2)
Step S3 is a step of mass spectrometry, preferably FT-ICR-mass spectrometry, for each fragment ion generated by the collision-induced dissociation of step 2 to specify the structure and abundance ratio of the cores constituting each fragment ion. be.

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

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

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

iv. Selection from the core structure list In the core structure list, there may be a plurality of items such as "the molecular weight, the DBE value, and the type and number of heteroatoms are all the same, but the structural formulas are different". In this case, a rule may be appropriately determined as to which of the plurality of them is selected as the first priority. For example, the following 1 to 3 can be mentioned as the priority.
1. 1. Priority is given to those consisting only of aromatic rings.
2. Priority is given to those with many unsaturated bonds.
3. 3. Priority is given to those with a small number of rings.

(B) Next, a method of specifying the abundance ratio of each core will be described.
As described above, the m / z, that is, the abundance ratio of the core having the mass can be obtained from the height of each peak obtained after the collision-induced dissociation in step S2.
The structure of each core after collision-induced dissociation obtained in this step 3 will be used later in step 5, and the abundance ratio of each core after collision-induced dissociation will be used later in step 4. It will be.

Step S4 (estimation of core existence mode and existence ratio for each class) (S4 in FIG. 2)
Molecules belonging to each of the peaks in step S1 are divided into "classes" based on "type and number of heteroatoms (including zero) and DBE value", and all molecules belonging to each "class" are classified. , A step of estimating its existence mode and existence ratio.
In other words, for the molecules belonging to all the peaks in step S1, the "class" is based on the "type and number of heteroatoms (including zero) and DBE value" in each molecular formula specified in step S1. This is a step of estimating the abundance mode and abundance ratio of all the molecules belonging to each of the "classes".

Hereinafter, step S4 will be described in detail.
(A) Since the molecular formulas are specified for all the peaks in step S1, the types and numbers of heteroatoms in the molecular formulas and the DBE value are known. Therefore, in this step, based on this "heteroatom type and its number and DBE value", each molecule assigned to all peaks is grouped by "heteroatom type and its number and DBE value". Incorporate into each "class".
The "type and number of heteroatoms" is, in detail, "the number of heteroatoms for each type of heteroatom". Since the hetero atom is preferably a nitrogen atom, a sulfur atom and an oxygen atom, the "type and number of hetero atoms" is preferably "the number of each of the nitrogen atom, the sulfur atom and the oxygen atom". You can also. Therefore, when it comes to heteroatoms, "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". In addition, in this specification, when it contains two nitrogen atoms, it may be referred to as "N2 class".

(B) Next, in each class enclosed in "type and number of heteroatoms and DBE value" described in (a), it is estimated what kind of single core or multi-core each molecule belonging to that class is. .. In addition, it is estimated at what ratio each of these single cores and multi-cores exists.
In making these estimates, it is preferable to make some assumptions for the convenience of actual calculation.
Here, there may be various combinations of "multi-core" depending on what kind of cores are cross-linked and connected. However, the sum of the DBE values of the plurality of cores forming the multi-core and the sum of the numbers according to the types of heteroatoms are all the same values for those 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 consisting of 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 these single cores or multi-cores are composed of will be described below.

When the molecule belonging to the class is a single core, the single core having the type and number of heteroatoms corresponding to the class and the DBE value is applicable. When the molecule belonging to the class is a multi-core, the sum of the numbers for each heteroatom of the same type existing in the plurality of cores constituting the multi-core and the sum of the DBE values of the plurality of cores are the sum of the DBE values. A combination of cores is applicable so as to match the type and number of heteroatoms in the class and the DBE value. Since it is sufficient that the sum of the numbers and the sum of the DBE values according to the types of heteroatoms of the plurality of cores corresponds to the types and numbers of the heteroatoms of the class and the DBE values, a combination of a plurality of cores constituting the multi-core Is usually not limited to one, but there are several types.

(D) Next, it is estimated "what proportion of each molecule belonging to the class, single core and multi-core, exists".
Preferably, first, it is assumed that the abundance ratio of the multi-core is the product of the abundance ratio of each of the plurality of cores constituting the multi-core, and this is used as an estimated value.

Step S5 (determination of core structure, side chain and cross-linking) (S5 in FIG. 2)
Step S5 is a step of determining the structure of the cores constituting the molecules whose existence modes are presumed in step S4, and further determining and allocating the side chains and crosslinks.

(A) For "each molecule whose existence mode is presumed in step S4", "determining the structure of the core forming them" is performed by the following operations i to iii.
i. In the case of the multi-core whose existence mode is estimated in step S4, it is divided (released) for each of the constituent cores.

ii. For all of the cores presumed to be single-core in step S4 and the cores generated by canceling the multi-core as in i above, for each of the same "type and number of heteroatoms and DBE value", respectively. Regrouped into "class". Incidentally, the "class" referred to here is a concept relating to the core obtained by canceling the original single core and multi-core, and is different from the "class" relating to the molecule described in step S4.

iii. With respect to all the "classes" of the "heteroatom type and number and DBE value" enclosed in ii above, a concrete structure is assigned to all the cores existing in the "class".

(A) The side chains and crosslinks are further determined by the following operations i to iii.
i. From the above, the structure of the core part of the single core or multi-core could be specified, but only assuming the existence of the core part, the target sample was obtained by FT-ICR-mass spectrometry. It does not match the mass indicated by the peak m / z. That is, even if the masses based on carbon, hydrogen, and heteroatoms involved in the core portion are totaled, there is a difference from the mass indicated by m / z of the peak obtained by FT-ICR-mass spectrometry.
Therefore, it is considered that the difference in mass is derived from the existence of the side chain bonded to the core and the crosslinks connecting the cores, and the number of carbons and the number of hydrogens are calculated so that the difference is eliminated. Allocate it to the core as side chains and crosslinks.
For example, it is assumed that a double core formed by cross-linking core 1 and core 2 is assigned to a 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 i above, the number of carbons and the number of hydrogens to be allocated as side chains and crosslinks are obtained, but the structure of the side chains and crosslinks has not yet been determined. Therefore, in estimating what kind of structure the side chains and crosslinks correspond to, for example, the following rules are determined in consideration of the existence probability of the expected combination of side chains and crosslinks, and according to the following rules. You can estimate it. As a rule, conditions such as the upper limit of the number of carbons constituting the side chains and crosslinks and the number of side chains may be set in advance.
iii. In the above i, if there is no side chain or crosslink corresponding to the difference in mass, the structure in which the core 1 and the core 2 are simply bonded may be applied.
(C) “Assigning” the side chain and the crosslink determined above to the core does not include determining which core and the position where the side chain and the crosslink are bonded.

(D) In this way, in step S5, for each single core or double core whose existence mode is presumed in step S4, the structure of the cores constituting them can be determined, and the side chain and cross-linking can be further determined. can.

By the above steps S1 to S5, the molecular structure of each component constituting the multi-component mixture can be specified by JACD, and the abundance ratio thereof can be specified.

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

In performing the fractionation, the standard used as the boundary of the fractionated object or the method for fractionation is not particularly limited. Specifically, it is preferable to carry out by the following method.
This is a method in which a multi-component mixture is subjected to a highly accurate type-specific separation pretreatment and fractionated into a plurality of components. Especially in the case of heavy oil, it is preferable to carry out such fractionation. The method of "separation pretreatment by type" is not particularly limited and may be separated into several components according to an arbitrary standard. However, a column chromatography fractionation method, a Soxhlet extraction method or a high-speed solvent extraction method A known method such as a solvent extraction method such as the above may be used. In the case of heavy oil, it is preferable to use a column chromatographic fractionation method, for example, as in the method described in Japanese Patent Application Laid-Open No. 2011-133363. The number of components to be fractionated may be appropriately selected according to the purpose.

Specifically, a method including the following first to fourth steps can be mentioned.
(First step)
The heavy oil is separated into marten (Ma) soluble in n-paraffin such as heptane and other insoluble components.
(Second step)
The malten content separated in the above (first step) is saturated using column chromatography (Sa), 1-ring aromatic component (1A), 2-cyclic aromatic component (2A), and 3 or more ring aromatic components (Sa). 3A +), polar resin (Po) and polycyclic aromatic resin (PA) are separated into fractions.
(Third step)
More preferably, the aromatic fractions (3A +) having three or more rings obtained in the second step are further subjected to preparative liquid chromatography to further obtain Peri-type tetracyclic aromatics and Cata-type tetraaromatics. Fractions and, in some cases, 5 or more rings of aromatics (5A +) may be separated.
(4th step)
Further, the insoluble matter separated in the above (first step) is separated into a toluene-soluble toluene-soluble component (alphalten (As)) and other toluene-insoluble matter (TI), and further, the toluene-insoluble matter is added. , THF soluble content soluble in THF and other THF insoluble content are separated.

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

Next, the steps for obtaining the melting point and Hansen solubility index value of the multi-component mixture in the present embodiment will be described.
Step S6 (Acquisition of melting point and Hansen solubility index value) (S6 in FIG. 2)
In steps S1 to S5, 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 multi-component mixture specified using JACD.
These physical property values are preferably specified by using the total petroleum molecule database (Comcat) for the molecular structure of each component of the multi-component mixture specified as described above.

Comcat is a "JACD-physical characteristic value database" in which JACD and each physical characteristic value are linked. The number of molecules registered in the database is about 25 million, and all the components contained in petroleum can be used in the model system analysis assuming that all the components contained in Comcat are composed of the 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, and polarization rate. , Ionization potential, heat of formation, enthalpy, entropy, free energy, heat capacity, etc., which are about 200 kinds of physical property values.

These physical property values are usually calculated using the atomic group contribution method or the molecular orbital method. In the atomic group contribution method, when determining the physical property value of a substance, the chemical structure of the substance is specified, and the substance is based on the unique parameter values of various existing atomic groups, that is, "groups". It is a method of calculating the physical property value of. That is, it is premised that the "group" of the substance is specified. Also, in the molecular orbital method, it is premised that the "group" of the substance is first specified and the structure is specified based on the "group".
In the present invention, as described above, since various existing atomic groups are specified for each component constituting the multi-component mixture, the components are specified by using known unique parameter values of the various atomic groups. The physical property value of can be calculated. Further, since the abundance ratio of each component is also specified, if this abundance ratio is taken into consideration, it is possible to appropriately estimate the physical characteristic value of the entire multi-component mixture from the physical characteristic value of each component.

Step (2): Estimating the solid phase amount in the multi-component mixture based on the fraction, melting point and Hansen solubility index value of each component Next, referring to the flowchart of FIG. 3, the multi-component mixture in the present embodiment. Step (2) for estimating the amount of solid phase in the solid phase will be described. More specifically, the multi-component aggregation model (MCAM) on which the present invention is based will be described in the following steps S7 to S16.

Step S7 (Separation into liquid phase component and non-liquid phase component) (S7 in FIG. 3)
In steps S1 to S6 described above, the fraction, melting point and Hansen solubility index value of each component are acquired, and the desired temperature T is set.
Among the components constituting the multi-component mixture, a component having a melting point lower than the desired temperature T is classified as a liquid phase component, and a component having a melting point equal to or higher than the desired temperature T is classified as a non-liquid phase component.
Here, the desired temperature T is as defined above.

Step S8 (Calculation of average HSP value of the entire liquid phase) (S8 in FIG. 3)
For the HSP value of each component classified as a liquid phase component in step S7, the weighted average value of each component weighted by the volume fraction in the liquid phase is calculated as the average HSP value of the entire liquid phase. The volume fraction can be calculated by acquiring various information on physical properties such as density and molecular weight in advance for each component.

Step S9 (Calculation of difference in HSP value between the entire liquid phase and each non-liquid phase component) (S9 in FIG. 3)
The difference (Δδ) between the average HSP value of the entire liquid phase calculated in step S8 and the HSP value of each component in the non-liquid phase component is calculated.

Step S10 (Update of classification of each component based on Δδ) (S10 in FIG. 3)
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 S9, and each component reclassified as a liquid phase component is a non-liquid phase component. Is incorporated into the liquid phase component to renew the liquid phase component and the non-liquid phase component.
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.

Step S11 (Calculation of average HSP value of the entire liquid phase after update) (S11 in FIG. 3)
For the HSP value of each component in the liquid phase component after updating in step S10, the weighted average value of each component weighted by the volume fraction in the updated liquid phase is used as the average HSP value of the entire updated liquid phase. calculate.

Step S12 (repetition of steps S9 to S11) (S12 in FIG. 3)
Steps S9 to S11 are repeated until the final step where the non-liquid phase component reclassified as the liquid phase component in step S10 disappears.

Step S13 (Calculation of cohesion of non-liquid phase components) (S13 in FIG. 3)
The degree of cohesion D (hereinafter, also referred to as DAgg value) of the non-liquid phase component after renewal at the final stage at a desired temperature is calculated. Here, the degree of cohesion D is a numerical value set by the HSP value, the concentration, and the temperature, and can be expressed by the following formula 1. The degree of cohesion D means the threshold value of the solid phase and the aggregated phase, and from the viewpoint of improving the accuracy of the correlation between the amount determined to be the solid phase in the present invention and the amount of sediment in the sediment test, the degree of cohesion D is It is 1.2 or more, preferably 2 to 3.

Step S14 (Classification of non-liquid phase components based on cohesion, estimation of solid phase amount) (S14 in FIG. 3)
Each component in the non-liquid phase component after renewal in the final stage is classified into an agglomerated phase component and a solid phase component based on the degree of cohesion D, and the solid phase amount is calculated.

For example, the total fraction of each component classified as an agglutinating phase component is calculated as an agglutinating phase fraction, and the total fraction of each component classified as a solid phase component is calculated as a solid phase fraction. Further, the value obtained by dividing the sum of the cohesive degrees of each component classified into the cohesive phase components by the number of the components is calculated as the average cohesive degree of the entire cohesive phase. By the above method, the solid phase amount can be estimated for this model heavy oil. At the same time, it is possible to calculate and estimate the amount of the liquid phase and the agglomerated phase in a solvent-free manner, their composition, the cohesion degree D of each molecule in the agglomerated phase, and the average agglomeration degree of the agglomerated phase by the above method. ..

The steps (1) and (2) described above may be carried out with reference to the methods described in Patent Documents 3 and 4, and these documents are referred to in the present specification by reference. Be part of the disclosure.

Step (3): Based on the physical property value information of at least one component selected from the precipitation-related component, the compatibility-related component, and the aggregation-related component in the multi-component mixture, the correction factor information in the estimation of the precipitation amount of the sediment is obtained by multivariate analysis. Steps to provide

In the method of the present invention, in addition to the estimated value of the solid phase amount of the multi-component mixture obtained in steps S1 to S14, at least one selected from the precipitation-related component, the compatibility-related component and the aggregation-related component in the multi-component mixture. Based on the physical property value information of the components, the correction factor information in the estimation of the precipitation amount of the sediment is provided by the multivariate analysis. It is a surprising fact that the amount of sediment precipitation can be predicted with high accuracy by matching the estimated values of the solid phase amount with the above-mentioned specific correction factor.

Precipitation-related components in the multi-component mixture used to provide the correction factor are preferably heptane insoluble, more preferably asphaltene (As) and toluene insoluble (TI).
The correction factor information based on the precipitation-related components in the multi-component mixture is preferably the amount information of heptane insoluble matter, and more preferably the amount information of asphaltene (As) and toluene insoluble matter (TI).

The compatibility-related components in the multi-component mixture used to provide the correction factor are preferably asphaltene and heptane-soluble components, more preferably asphaltene (As) and aromatic components (3 rings or more: 3A ^+). ) And polar resin (Po).
Further, the correction factor information based on the compatibility-related components in the multi-component mixture is preferably the amount information of the heptane insoluble component, more preferably asphaltene (As), the aromatic component (3 rings or more: 3A ⁺ ), and the polarity. It is the ratio information (As / 3A ⁺ + Po) with the sum of the resin (Po).

Further, as the aggregation-related component in the multi-component mixture used for providing the correction factor, an aromatic component containing two or more nitrogen atoms is preferable, and a monocyclic aromatic component and a bicyclic aromatic component are more preferable. It is an aromatic component containing two or more nitrogen atoms. It is a surprising fact that such aromatics can be used as a correction factor associated with agglutination.
Further, the correction factor information based on the compatibility-related components in the multi-component mixture preferably includes the amount information of the aromatic component containing two or more nitrogen atoms, and more preferably the monocyclic aromatic component (single core) and It is the amount information of the (N2 class) aromatic component which is a bicyclic (double core) aromatic component and contains two nitrogen atoms.

Further, according to a preferred embodiment of the present invention, in the method, in addition to the estimated value of the solid phase amount of the multi-component mixture obtained in steps S1 to S14, the precipitation-related component, the compatibility-related component and the aggregation-related in the multi-component mixture. Based on the physical property value information of the adult, the correction factor information in the estimation of the precipitation amount of the sediment is provided by the multivariate analysis. The correction factor provided based on the physical property value information of the three components of the precipitation-related component, the compatibility-related component, and the agglutination-related composition in the multi-component mixture is particularly advantageous in improving the accuracy in estimating the precipitation amount of the sediment.

According to a more preferable aspect of the present invention, the amount of sediment precipitation can be corrected by the following formula 2.

In Equation 2, a to f and T are constants.
The amount of As is the amount of asphaltene,
The amount of TI is the amount of toluene insoluble,
As / (3A ⁺ + Po) is the amount of asphaltene (mass%) / (aromatic content (3 rings or more) amount (mass%) + polar resin amount (mass%)).
The N2 class fraction (double core) is the amount (mass%) of a single ring aromatic containing two nitrogen atoms.
The N2 class fraction (single core) is the amount (mass%) of the bicyclic aromatic component containing two nitrogen atoms.

In Equation 2 above, the constants a to f and T can be set by multivariate analysis using known software such as Excel. Further, each amount of As, 3A ⁺ Po, N2 class fraction (double core), and N2 class fraction (single core) can be set based on the measured value of the above mass spectrometry or the average value thereof.

Step (4): Matching the amount of sediment precipitation in the multi-component mixture based on the solid phase amount and the correction factor information Next, in the method of the present invention, based on the solid phase estimated value by MCAM and the above-mentioned compensating factor information. , The amount of sedimentation in the multi-component mixture is matched to estimate the amount of sedimentation. The estimation of the amount of sediment deposited can be carried out by using the method or formula described in step (3) above.

According to a preferred embodiment of the present invention, the prediction of the amount of sediment deposited can be suitably used in a petroleum hydrocracking apparatus.

The multi-component mixture is preferably petroleum, more preferably heavy oil, but is not limited to these as long as it is a multi-component mixture.

The method for estimating the amount of sediment deposited in the present invention can be used for setting the operating conditions of the device for the multi-component mixture from the viewpoint of preventing fouling. Therefore, according to a preferred embodiment of the present invention, there is provided a method of operating an apparatus for a multi-component mixture in which operating conditions are set based on an estimated sedimentation amount of sediment estimated by the above method.

<Devices and systems for estimating the amount of sedimentation of multi-component mixtures>
Next, an embodiment of a sediment precipitation amount estimation device in the multi-component mixture of the present invention will be described with reference to FIG. FIG. 4 is a functional block diagram of the sedimentation amount estimation device for the multi-component mixture of the embodiment. By causing the computer to execute the program of the present invention, the computer functions as a sediment deposition amount estimation device.
Note that FIG. 4 omits the illustration of an interface for inputting and outputting information.

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

The arithmetic unit 1 includes a component information providing unit 10, a solid phase amount estimating unit 20, a correction factor information providing unit 30, and a sediment precipitation amount estimating unit 40.

I. Ingredient Information Providing Unit The ingredient information providing unit 10 acquires the fraction, melting point, and HSP value of each component constituting the target multi-component mixture. The information on these components may be obtained from the storage unit 2 in which the information about the multi-component mixture is stored as a database.

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

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

(1) In this method, it is first 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 do not mean strictly all the molecular species existing in the solution, but the molecules having a certain abundance (absence ratio) or more in the solution. You can think of it as a species. It is desirable to target as many molecular species as possible in the solution, but molecular species that are present in trace amounts can be ignored. The component of the solution as a sample may be analyzed in advance, and the abundance (absence ratio) of each molecular species may be used as a criterion for selecting the target molecular species.

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

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

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

II. Solid phase amount estimation unit The solid phase amount estimation unit 22 includes an initial classification unit 21, a liquid phase calculation unit 22, and a non-liquid phase calculation unit 23.

The initial classification unit 21 classifies the components having a melting point below the desired temperature among the components constituting the multi-component mixture as liquid phase components, and classifies the components having a melting point above the desired temperature as non-liquid phase components. do. That is, at an arbitrary temperature equal to or higher than the melting point of the solvent, the amount and composition of the "liquid phase" at that temperature are determined. A component having a melting point lower than that temperature is a component existing in the liquid phase. The amount and components of the "liquid phase" at this time can be obtained.

The liquid phase calculation unit 22 includes an average HSP calculation unit 221 and a Δδ (HSP value difference) calculation unit 222, a reclassification unit 223, and a liquid phase component information calculation unit 224 in order to estimate the properties of the liquid phase. I have.

The average HSP calculation unit 221 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 the volume fraction. be.

The HSP value difference (Δδ) calculation unit 222 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 reclassification unit 223 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 each component reclassified as a liquid phase component is non-liquid. Incorporate from the phase component to the liquid phase component to renew the liquid phase component and the non-liquid phase component.
The reclassification unit 223 adds the dissolved component, if any, to the liquid phase and recalculates the HSP value of the entire liquid phase.

The average HSP calculation unit 221 calculates the average HSP value of the entire liquid phase after the update. Here, the average HSP value of the entire updated liquid phase is a weighted average value obtained by weighting the HSP value of each component in the updated liquid phase component by the fraction of each component in the liquid phase, preferably the volume fraction. It is calculated.

Then, the average HSP value, the liquid phase component, and the non-liquid phase component (aggregated phase, solid phase) are repeatedly updated until the final stage where the non-liquid phase component reclassified as the liquid phase component disappears.

Further, the liquid phase information calculation unit 224 calculates the total fraction of the liquid phase components after the update at the final stage as the liquid phase fraction.

The non-liquid phase calculation unit 23 has a cohesion degree calculation unit, a cohesive phase, a solid phase classification unit, an agglomerated phase information calculation unit, and a solid phase information calculation unit, although not shown, for estimating the amount of the solid phase amount. Is preferable. The non-liquid phase calculation unit determines, for example, the amount of agglomerated phase, the component, the degree of cohesion of each of the agglomerated components, the average degree of cohesion of the agglomerated phase, and the amount and composition of the solid phase as the properties of the non-liquid phase.

The cohesion degree calculation unit determines the degree of cohesion of each component in the non-liquid phase component after renewal at the final stage at a desired temperature by the average HSP value of the entire liquid phase and the HSP value of each component in the non-liquid phase component. Calculated based on the difference and the concentration C of each component in the non-liquid phase component after renewal at the final stage.
Specifically, they are classified as follows.

For each component in the non-liquid phase component that is not finally dissolved in the liquid phase, the degree of cohesion of each component is determined based on the HSP value and the HSP value of the entire liquid phase. The degree of cohesion D of each of the agglomerated components is calculated by the functional formula (A) with variables of 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. 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)

In the formula, 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 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, 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, where C is the concentration of the aggregated component in the non-liquid phase component.

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

K _{0 to} K ₉ are empirically obtained coefficients and have the following constant values.
K ₀ = -1.26929,
K ₁ = 9.42231,
K ₂ = 0.363439,
K ₃ = -11.192,
K ₄ = 0.093322,
K ₅ = -0.15436,
K ₆ = 5.3374333,
K ₇ = -0.20868,
K ₈ = 0.077223,
K ₉ = 0.019492
Is.

From the above, when a certain component is agglomerated in a certain solution at a certain temperature, the value of the degree of cohesion D of the agglomerated component can be calculated.
The values of L ₀ , L _1, L _2, M _AS, K _{0 to} K _9, etc. shown in the above numerical values can be various numerical values depending on the object and are limited to the above numerical values. is not it.

Of the non-liquid phase components after renewal in the final stage, the agglomerated phase and solid phase classification units classify the components having a degree of cohesion less than a predetermined threshold value as the cohesive phase components, and the components having a degree of cohesion greater than or equal to a predetermined threshold value. Classify as a solid phase component. That is, a component having a degree of cohesion at the cohesion level is a cohesive phase component, and a component having a precipitation level is a solid phase component. Here, "at the agglomeration level" conceptually means that the size of the agglomerated particles is several hundred nm or less and is dispersed in the liquid, and "at the precipitation level" means that the agglomerated particles are dispersed in the liquid. It is considered that the size of the particles is submicron or larger and cannot be dispersed in the liquid and is precipitated. When the degree of cohesion D ≧ 5, it can be generally determined that the component species are precipitated, but this threshold value can be changed depending on the component species.

The agglutination phase information calculation unit calculates the total amount of each component classified as the agglutination phase component (parts per fraction of the entire solution) as the agglutination phase fraction. Further, the cohesive phase information calculation unit calculates a value obtained by dividing the sum of the cohesive degrees of each component classified as the cohesive phase component by the number of the components as the average cohesive degree of the entire cohesive phase.

The solid phase information calculation unit calculates the total amount of each component classified as a solid phase component (parts to the entire solution) as the solid phase fraction, and further estimates the solid phase amount from the solid phase fraction and the total amount. Calculate the value.

III. Correction factor information providing unit The correction factor information providing unit makes corrections in estimating the precipitation amount of sediments based on the physical property value information of at least one component selected from the precipitation-related component, the compatibility-related component, and the aggregation-related component in the multi-component mixture. Factor information is provided by multivariate analysis.

Whether to use a part or all of the precipitation-related component, the compatibility-related component, and the aggregation-related component can be appropriately selected and set by those skilled in the art. Specific types and preferred embodiments of the precipitation-related component, the compatibility-related component, and the aggregation-related component are the same as those described above.

In addition, the correction factor information providing unit provides correction factor information based on the actually measured values input for the precipitation-related component, the compatibility-related component, and the aggregation-related component. For example, the correction factor information providing unit can calculate at least one or all information about a predetermined constant, quantity, and ratio described in the above equation 2 by multivariate analysis based on actual measurement values.

IV. Sediment Precipitation Estimate Section In the Sediment Precipitation Estimate Section, the solid phase amount estimation value provided by the solid phase amount estimation section and the correction factor information provided by the correction factor information providing section are matched to match the sediment's precipitation amount estimation section. Estimate the amount of precipitation. The amount of sediment deposited can be calculated based on, for example, Equation 2. The sedimentation amount estimation unit of the sediment may be integrally configured with the correction factor information providing unit.

Further, each part of the sediment precipitation amount estimation device of the present invention may be integrally formed, but each part may be formed as a separate body if desired. When the sediment precipitation amount is estimated by such independent parts, the sediment precipitation amount estimation device can be provided as a system for estimating the sediment precipitation amount.

Therefore, according to another aspect of the present invention, it is a system for estimating the amount of sedimentation in a multi-component mixture.
A component information providing unit that provides fractions, melting points, and Hansen solubility index values of each component based on the molecular structure information of each component constituting the multi-component mixture.
Phasor amount estimation unit that estimates the solid phase amount in a multi-component mixture based on the fraction, melting point, and Hansen solubility index value of each component.
Correction factor information that provides correction factor information in estimating the precipitation amount of a sediment by multivariate analysis based on the physical property value information of at least one component selected from the precipitation-related component, the compatibility-related component, and the aggregation-related component in the multi-component mixture. A system is provided that includes at least a supply unit and a sediment precipitation estimation unit that matches the sediment precipitation amount in a multi-component mixture by multivariate analysis based on the solid phase amount and correction factor information.

<Characteristic estimation program for multi-component mixture>
In the present invention, a series of processing of estimating the molecular structure using JACD, associating the estimated molecular structure information with the physical property value, and estimating the property of the multi-component mixture using the aggregation model is 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 and execute it, or install the program 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. Further, the program can be temporarily or permanently stored (recorded) in a removable recording medium such as a flexible disk, a CD-ROM, an MO disk, a DVD, a magnetic disk, or a semiconductor memory.

In addition to installing the program on the computer from the removable recording medium as described above, the program can be wirelessly transferred to the computer from the download site, or can be transferred to the computer by wire via a network such as LAN or the Internet. Then, the program transferred in this way can be received and installed on a recording medium such as a built-in hard disk.

The method of the present invention can be suitably carried out on a computer in which the above computer program is stored in an internal storage device.

Further, the various processes described in the present specification are not only executed in chronological order according to the description, but may also be executed in parallel or individually as required by the processing capacity of the device that executes the processes. .. Further, in the present specification, the system is a logical set configuration of a plurality of devices, and the devices of each configuration are not limited to those in the same housing.
Although the embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the present invention. Further, in the above-described embodiment, FT-ICR-mass spectrometry is used as the mass spectrometry, but the present invention is not limited thereto.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Test Example 1
As a sample, the sample No. which is the vacuum residual oil (VR) (corresponding to heavy oil) obtained by distilling the atmospheric residual oil under reduced pressure. 1 to 8 were used. Samples were separated by solvent extraction and column chromatography according to the procedure shown below. As shown in FIG. 5, the separated fractions are saturated (Sa), three aromatics (1A, 2A, 3A +), polar, polycyclic resin (Po, PA), ammonium (As), and the like. And it is a THF-soluble component and a THF-insoluble component in the toluene insoluble component (TI).

Saturated components (Sa), 1-ring aromatics (1A), 2-cyclic aromatics (2A), obtained by performing the pretreatment method (1st and 2nd steps) on the reduced pressure residual oil (VR). About each fraction of three or more rings of aromatic (3A +), polar resin (Po) and polycyclic aromatic resin (PA), and each fraction of asphaltene (As) separated from marten in the first step. , The profit rate of each was calculated.

(First step: Separation of marten)
7 g of the sample was weighed in an Erlenmeyer flask having a capacity of 500 ml, 220 ml of n-heptane was added, an air cooling tube was attached, and the mixture was boiled at reflux for 1 hour in an n-heptane insoluble matter tester.
After reflux boiling, the mixture was allowed to cool, and the insoluble heptane was separated using a filter paper to obtain a fraction containing marten.

(2nd step and 3rd 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 x 600 mm (gel-filled part, made of glass)
Gel: Silica gel 40g + Alumina gel 50g (after activation)
Silica gel: Chromato Gel Grade 923AR, manufactured by Fuji Silysia
Alumina gel: MP BiomebicaLs, MP Alumina, Activated, Neutral, Super I
Activation conditions: Silica gel 250 ° C. x 20 h, Alumina gel 400 ° C. x 20 h, 0.2 kg / cm ² (N ₂ gas) Pressurized Sample amount: 1.5 g (Marten)

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

(4th step)
220 ml of toluene was added to the insoluble heptane separated in the first step, an air cooling tube was attached, and the mixture was boiled under reflux for 1 hour. After boiling under reflux, the mixture was allowed to cool, and the insoluble toluene was separated using a filter paper to obtain a soluble toluene (asphaltene: As).
Further, 220 ml of THF was added to the toluene insoluble matter (TI), an air cooling tube was attached, and the mixture was boiled under reflux for 1 hour. After boiling under reflux, the mixture was allowed to cool, and a THF-insoluble component was separated using a filter paper to obtain a THF-soluble component.

Fractions were measured with an FT-ICR MS (solariX 12T, manufactured by Bruker Daltonix) equipped with a 12 Tesla superconducting magnet. The ionization methods are atmospheric pressure photoionization (APPI), which can efficiently ionize aromatic components, and laser desorption ionization (LDI), which has high sensitivity of polycyclic aromatic molecules and can measure even toluene insolubles. The method was used. Peak detection, internal calibration, and identification of the molecular formula were performed using Composer (manufactured by Sierra Analytics). From the obtained molecular formula, the Hansen solubility (HSP) was obtained from the above-mentioned structural analysis and the estimation method by the atomic group contribution method, and the components of the liquid phase, agglutinated phase, and solid phase were predicted by MCAM.

Table 2 shows the fractionation results and the results of calculating the solid phase by MCAM for various produced oils together with the sediment test results.

Fouling The cell displayed as "high" is a sample in operation where the differential pressure due to fouling in the heat exchanger is high, and the amount exceeding 1% by mass was detected even in the sediment test (measured result of sediment). Has been done. On the other hand, in the low fouling sample labeled as fouling "low", the amount was 0.5% by mass or less in the sidiment test, and the difference between the two is clear.

On the other hand, regarding the result of MCAM calculation, the correlation between the solid phase and the sediment test is shown in FIG. 6 as a scatter diagram. As can be seen from the graph, it can be seen that the quantitative correlation between the sediment test and the MCAM solid phase is low.

Test Example 2
Based on the analysis results of Test Example 1, it was examined to newly construct a precipitation amount prediction formula considering a plurality of factors including the MCAM calculation results as described below.

For the factors considered in the sediment amount prediction formula, parameters were selected from the following three viewpoints in addition to the solid phase amount in the MCAM calculation.
(A) Correction factor for the amount of components precipitated as a sediment: Alfaluten (As) and toluene insoluble (TI) amount in the fractionation result (B) Correction factor for the compatibility of the sediment: As and 3A ⁺ + Po in the fractionation result Ratio (As / (3A ⁺ + Po))
(C) Structural factors affecting sediment aggregation: Mole fraction per core of N2 class in aggregate phase + solid phase in MCAM

(A) Correction factor information based on physical property value information of precipitation-related components: As and TI amount information (A) is detected by FT-ICR MS such as THF insoluble components in addition to the points considered to be components of sediment. Since it contains molecules that are difficult to be treated, it was taken up as a correction factor. The relationship with the amount of sediment is shown in FIGS. 7 and 8. Both the amount of As and the amount of TI are loosely correlated with the amount of sediment.

(B) Correction factor information based on physical property value information of compatibility-related components: Regarding the ratio information (B) of asphaltene and the sum of aromatics and polar resins, as shown in FIG. 9, the number of carbon atoms in the produced oil is 40. It was confirmed that the amounts of the components having a degree of unsaturation of ~ 60 and a degree of unsaturation of 10 to 20 affected the dissolution of the precipitate, and the main component thereof was 3A ⁺ + Po.

The relationship between the amount of sediment and As / (3A ⁺ + Po) is shown in FIG. It was found that there was a gradual but relatively good correlation with the amount of sediment in the sediment test.

(C) Correction factor information based on physical property value information of aggregation-related components: Regarding the amount information of aromatics containing two or more nitrogen atoms (C), in Table 1, the amount of sediment in the sediment test and the solidification in MCAM. No correlation was found in any of the phase amount, As amount, and TI amount. Regarding 7 and 8, N-class analysis was performed for each category of DAgg value for each core in the aggregated phase + solid phase in MCAM, and the tendency was examined. It was found that the N2 class abundance ratio was higher in the sample 7 having a large amount of sediment than in the sample 8.

The relationship between the amount of sedimentation and the N2 class fraction for each of the double core and the single core is shown in FIGS. 11 and 12. It was found that there was a gradual but relatively good correlation with the amount of sediment in the sediment test. Although it is only a relative comparison, it seems that the double core has a better correlation than the single core, and the double core has a greater effect on the amount of sediment generated.

From the above results, the assumed factors are correlated with the amount of sediment, but since they are all loosely correlated, the precipitation prediction formula shown in Equation 2 should be created by multivariate analysis combining these factors. And said.

Based on the above formula 2, sample No. Using the data from 1 to 8, multiple regression calculations were performed to create a formula for predicting precipitates, and the constants were determined. Comparing the obtained predicted amount of sediment precipitation according to Equation 2 with the actually measured amount of sediment, it becomes as shown in FIG. 13, and by plotting it on a line showing a 1: 1 correlation, it is possible to create a predicted formula with improved accuracy. I arrived.

As described above, in addition to the MCAM solid phase, As and TI of the fractionation result are used as correction factors for the amount of components precipitated as sediments, and the ratio of As and 3A ++ Po of the fractionation results are used as correction factors for the compatibility of sediments. As a structural factor influencing aggregation, the mole fraction of each N2 class core in the aggregated phase + solid phase in MCAM was selected. It was confirmed that the amount of sediment can be predicted with high accuracy by using a prediction formula that incorporates factors that affect such precipitation.

According to the present invention, by combining the estimation information of the solid phase amount of the multi-component mixture obtained from the multi-component aggregation model using a computer with the specific correction factor information, the amount of sedimentation in the multi-component mixture can be highly accurate. Can be estimated with. Furthermore, estimating the amount of sediment deposited in the multi-component mixture with high accuracy contributes to dramatically improving the operational stability and operational efficiency of the petroleum refining equipment.

Claims (20)

A computer-based method for estimating the amount of sediment deposited in a multi-component mixture.
(1) A step of providing a fraction, melting point and Hansen solubility index value of each component based on the molecular structure information of each component constituting the multi-component mixture.
(2) A step of estimating the solid phase amount in the multi-component mixture based on the fraction, melting point and Hansen solubility index value of each component.
(3) Based on the physical property value information of at least one component selected from the precipitation-related component, the compatibility-related component and the aggregation-related component in the multi-component mixture, the correction factor information in the estimation of the precipitation amount of the sediment is provided by multivariate analysis. And (4) a step of matching the amount of sediment precipitation in the multi-component mixture based on the solid phase amount and the correction factor information. The claim that in step (3), based on the physical property value information of the precipitation-related component, the compatibility-related component, and the aggregation-related component in the multi-component mixture, the correction factor information in the estimation of the precipitation amount of the sediment is provided by multivariate analysis. The method according to 1. The method according to claim 1 or 2, wherein the precipitation-related component is a heptane insoluble component. The method according to any one of 1 to 3, wherein the precipitation-related component is asphaltene and toluene insoluble. The method according to any one of claims 1 to 4, wherein the compatibility-related component contains asphaltene and heptane-soluble components. The method according to any one of claims 1 to 5, wherein the compatibility-related component is asphaltene, an aromatic component, and a polar resin. The method according to any one of claims 1 to 6, wherein the aggregation-related component is an aromatic component containing two or more nitrogen atoms. The method according to claim 7, wherein the aromatic component containing two or more nitrogen atoms contains a monocyclic aromatic component and a bicyclic aromatic component. The method according to any one of claims 1 to 8, wherein the correction factor information includes information on the amount of asphaltene and toluene insoluble. The method according to any one of claims 1 to 9, wherein the correction factor information includes ratio information of asphaltene and the sum of aromatics and polar resins. The method according to any one of claims 1 to 10, wherein the correction factor information includes information on the amount of an aromatic component containing two or more nitrogen atoms. The method according to any one of claims 1 to 11, wherein the multi-component mixture is petroleum. The method according to any one of claims 1 to 12, wherein the multi-component mixture is a heavy fraction. The method according to any one of claims 1 to 13, wherein the amount of sediment deposited is the amount of sediment deposited in a petroleum hydrocracking apparatus. A method for operating an apparatus for a multi-component mixture, wherein operating conditions are set based on an estimated sedimentation amount of sediment estimated by the method according to any one of claims 1 to 14. A device for estimating the amount of sedimentation in a multi-component mixture.
A component information providing unit that provides a fraction, a melting point, and a Hansen solubility index value of each component based on the molecular structure information of each component constituting the multi-component mixture.
A solid phase amount estimation unit that estimates the solid phase amount in the multicomponent mixture based on the fraction, melting point, and Hansen solubility index value of each component.
A correction factor that provides correction factor information in estimating the precipitation amount of a sediment by multivariate analysis based on the physical property value information of at least one component selected from the precipitation-related component, the compatibility-related component, and the aggregation-related component in the multi-component mixture. An apparatus including at least an information providing unit and a sediment precipitation amount estimation unit that matches the sediment precipitation amount in a multi-component mixture based on the solid phase amount and the correction factor information. A system for estimating the amount of sedimentation in a multi-component mixture.
A component information providing unit that provides a fraction, a melting point, and a Hansen solubility index value of each component based on the molecular structure information of each component constituting the multi-component mixture.
A solid phase amount estimation unit that estimates the solid phase amount in the multicomponent mixture based on the fraction, melting point, and Hansen solubility index value of each component.
A correction factor that provides correction factor information in estimating the precipitation amount of a sediment by multivariate analysis based on the physical property value information of at least one component selected from the precipitation-related component, the compatibility-related component, and the aggregation-related component in the multi-component mixture. A system including at least an information providing unit and a sediment precipitation amount estimation unit for matching the sediment precipitation amount in a multi-component mixture by multivariate analysis based on the solid phase amount and the correction factor information. A computer program for executing the method according to any one of claims 1 to 15, the apparatus according to claim 16, or the system according to claim 17. A computer-readable recording medium on which the computer program according to claim 18 is recorded. A computer in which the computer program according to claim 19 is stored in an internal storage device.

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