JP2022155376A - Estimation method for coke generation amount in fluid catalytic cracking device - Google Patents

Abstract

To provide a new method for estimating a coke generation amount with high precision in a fluid catalytic cracking device.SOLUTION: A method for estimating a coke generation amount in a fluid catalytic cracking device by a computer includes the steps of: (1) obtaining component information of a single core molecule in raw material oil based on results of raw material oil analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS); and (2) calculating the coke generation amount based on the component information on the single core molecule whose total number of rings is four or more and naphthene ring number is two or more and the single core molecule whose total number of rings is seven or more and the naphthene ring number is one or less.SELECTED DRAWING: Figure 5

Description

There is an application for the application of Article 30, Paragraph 2 of the Patent Act. Publication name FY2019 Research and development project related to structural analysis and reaction analysis of petroleum, which is the basis of highly efficient petroleum refining technology Business report 2. Date of issue March 31, 2020 3. Publisher Japan Petroleum Energy Technology Center [Publications] 1. Posting address http://www. pecj. or. jp/forum http://www. pecj. or. jp/japanese/jpecforum/2020/pdf/jf016. pdf 2. Posting date May 11, 2020 3. Publisher: Kiyoshi Sase [Publications] 1. Posting address, etc. https://www. pecj. or. jp/wp-content/uploads/2021/02/JPEC_report_No. 210201. pdf On the same day, it will also be sent by e-mail to the person in charge of the supporting member company of the Japan Petroleum Energy Technology Center. Posted on February 12, 2021 3. Publisher Japan Petroleum Energy Technology Center [Publications] 1. Name of Meeting Kumamoto Meeting of Japan Petroleum Institute (50th Petroleum and Petrochemical Symposium) ２． Date November 13, 2020 3. Published by Kotaro Matsumoto [Publications] 1. Posting address https://conf. atlas. jp/guide/event/jpi2020f/top2. Posting date November 10, 2020 3. Published by Kotaro Matsumoto [Publications] 1. Posting address https://conf. atlas. jp/guide/event/jpi2020f/proceedings/list2. Posting date February 1, 2021 3. Published by Kotaro Matsumoto

The present invention relates to a method for estimating the amount of coke produced in fluid catalytic cracking units, and more particularly, a method for estimating the amount of coke produced in fluid catalytic cracking units such as RFCC by computer, and an apparatus used therefor. It relates to a system, a computer, a method of using the same, a computer program that causes a computer to execute the device, and a recording medium thereof.

Fluidized catalytic cracking is a reaction in which petroleum feedstocks such as heavy oil are brought into contact with a catalyst to crack them and convert them into high-value light oil, middle distillates, and the like. For fluid catalytic cracking, fluid catalytic cracking (FCC) units that mainly use desulfurized vacuum gas oil (DSVGO) as raw material, and residue fluid catalytic cracking (RFCC) units that mainly use desulfurized atmospheric residue (DSAR) as raw material, etc. Fluidized catalytic cracking units are widely used, and are positioned as the key to technological development to improve the profitability of refineries.

In fluidized catalytic cracking, deterioration of the reaction efficiency of the catalyst due to coke generation is often a problem, so the catalyst with coke attached is usually combusted in a regeneration tower, and the catalyst after combustion is reused. . Therefore, from the viewpoint of avoiding a decrease in the efficiency of fluidized catalytic cracking due to coke generation, various studies are conducted to estimate the amount of coke generation according to the properties of raw materials, the reaction conditions including the type of catalyst, etc., and to realize the optimum operation. is done. (For example, Patent Document 1).

JP 2017-66203 A

However, in fluidized catalytic cracking units, there have been no reports on the molecular structure and abundance of constituent components in the feedstock that can be used to predict the amount of coke produced. was difficult. In addition, it was generally thought that the heavier the raw material, the greater the amount of coke produced, but it is known that even the light raw material produces coke.

Under such technical circumstances, as a result of intensive studies, the applicant found that in estimating the yield of produced oil in fluidized catalytic cracking units, feedstock oil obtained by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) It was found that the amount of coke produced in fluidized catalytic cracking equipment can be estimated with high accuracy based on the specific component information of The present invention is based on such findings.

Accordingly, one object of the present invention is to predict the amount of coke produced in fluidized catalytic cracking apparatuses with high accuracy.

In order to achieve the above objects, the present inventors created the following inventions. That is, the gist of the present invention is as follows.
In one embodiment of the present invention, a computerized method for estimating coke production in fluid catalytic cracking units, comprising:
(1) obtaining constituent information of single core molecules in the feedstock based on the results of feedstock analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS); The amount of coke produced is calculated based on the component information of a single-core molecule having 4 or more and 2 or more naphthenic rings and a single-core molecule having 7 or more total rings and 1 or less naphthenic rings. It is characterized by including a step.

In another embodiment of the present invention, a coke production amount estimation device, a system, a method of operating them, a computer program for executing them, a recording medium thereof, and a computer storing it provided.

ADVANTAGE OF THE INVENTION According to this invention, it is a fluid-catalytic-cracking apparatus. WHEREIN: The amount of coke production can be estimated with high precision.

4 is a flow chart illustrating a method for computer estimation of the amount of coke produced in fluid catalytic cracking units according to an embodiment of the present invention. 1 is a flow chart explaining step (1) for identifying the molecular structure of each component of a multi-component mixture (feedstock oil) in an embodiment of the present invention. It is a functional block diagram explaining the estimation apparatus of the amount of coke production in the fluid catalytic cracking apparatus by embodiment of this invention. 1 is a schematic diagram of an RFCC bench apparatus used in accordance with an embodiment of the present invention; FIG. In an embodiment of the present invention, the amount of cores in feed oil and the amount of cores in product oil for single-core molecules with 4 or more total rings (Core 4-ring +) or single-core molecules with 5 or more total rings (Core 5-ring +) is a graph showing the correlation between the difference in , and the amount of coke produced.

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

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

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

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

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

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

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

(8) "Molecular formula"
A "molecular formula" is a formula that indicates only the types and numbers of elements that constitute a molecule, and indicates that the structure is not specified. Since the types and numbers of elements constituting the molecule are known, information such as the molecular weight and the DBE value, which will be 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-MS", the spectrum obtained by FT-ICR-mass spectrometry is "FT-ICR-mass spectrometry spectrum" ), the value of m/z can be determined to four decimal places. Therefore, the molecular formula of the molecule attributed to the peak can be determined by performing accurate mass number matching in consideration of the presence of atomic isotopes. Since the molecular formula only expresses the types and numbers of elements constituting the molecule, a molecule corresponding to the determined molecular formula may have a plurality of isomers. That is, multiple isomers having the same molecular formula can be attributed to one peak.

However, due to the characteristics of FT-ICR-MS, even if the molecular formula is the same, for example, hydrogen ions are added to the molecular ions, resulting in different masses from the original molecular ions. It may appear as a peak. Therefore, even if the peaks appear as different peaks in the measurement, those having the same kind and number of elements constituting the molecular formula may be regarded as "the same molecular formula". In the phrase "molecules corresponding to the molecular formula", "the molecular formula" may be understood to mean "the same molecular formula". In addition, the term "certain peak" may be considered as a concept that collectively captures all peaks of various m/z that represent "the same molecular formula" in the above sense.

(9) "core", "single core", "double core"
The “core” is a kind of “attribute” described in the “JACD” section below, and specifically includes an aromatic ring or a naphthene ring itself, an aromatic ring and a naphthene ring that are not bridged but directly bonded. or a hetero ring directly bonded to an aromatic ring or naphthenic ring instead of being bridged. A "core" means without any bridges or side chains, since the bridges or side chains are separate attributes from the core.

On the other hand, "single core" is a concept that indicates a molecule having only one core. Since it is a concept that refers to molecules, it also includes those in which side chains are bound to the core. A molecule in which two or more of the above cores are crosslinked is called a "multicore". Since "multicore" also means a molecule, it also includes those in which side chains are attached to the core. A molecule in which two cores are crosslinked is called a “double core”.
For example, the naphthalene molecule shown below is a "single core" because it consists of one aromatic ring, and is not a double core consisting of two benzene rings.

(10) "DBE value"
The " _DBE value" _is a value calculated by the following formula (1) when the _{molecular formula} is " _CcHhNnOoSs ".
DBE=c-h/2+n/2+1 (1)
(Wherein, c is the number of carbon atoms, h is the number of hydrogen atoms, n is the number of nitrogen atoms, o is the number of oxygen atoms, and s is the number of sulfur atoms.)
This value generally indicates the degree of unsaturation in the molecule, especially the presence of double bonds and rings.

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

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

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

(12) "Physical property value"
A "physical property value" is included in a "physical property value" regardless of its name as long as it expresses the physical or chemical properties, properties, or characteristics of a substance. As used herein, the term "physical property" includes, but is not limited to, boiling point, melting point, Hansen solubility index value, Gibbs free energy of formation, ionization potential, polarizability, dielectric constant, vapor pressure, Liquid density, API degree, gas viscosity, liquid viscosity, surface tension, critical temperature, critical pressure, critical volume, heat of formation, heat capacity, dipole moment, enthalpy, entropy and the like.

(13) “Oil”
As used herein, the term “petroleum” includes crude oil, fractions obtained by distilling crude oil, and fractions obtained by subjecting the fractions to secondary equipment such as reforming and cracking. A generic concept that includes Alternatively, it may refer to a fraction obtained by further fractionating a fraction obtained by distilling crude oil into components such as saturated hydrocarbons and aromatic hydrocarbons.

(14) “Fluid catalytic cracking unit”, “Fluid catalytic cracking units”
As used herein, the term "fluid catalytic cracking unit" refers to a unit that cracks a petroleum fraction by a fluid catalytic cracking reaction, and includes a fluid catalytic cracking (FCC) unit and a residue fluid catalytic cracking (RFCC) unit. In some cases, it is described as "fluid catalytic cracking equipment" to distinguish it from the narrowly defined fluid catalytic cracking (FCC) equipment.

<Method for estimating the amount of coke produced in fluid catalytic cracking equipment by computer>
According to one embodiment of the present invention, as shown in FIG. 1, a method for computationally estimating coke production in fluid catalytic cracking units, comprising:
(1) obtaining constituent information of single core molecules in the feedstock based on the results of feedstock analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS); The amount of coke produced is calculated based on the component information of the single-core molecule having 4 or more and 2 or more naphthenic rings and the single-core molecule having 7 or more total rings and 1 or less naphthenic rings. A method is provided that includes the step of: It is an unexpected fact that a single-core molecule as described above can serve as an index for estimating the amount of coke produced in fluid catalytic cracking units.

Step (1): Based on the results of feedstock analysis using FT-ICR MS, the step of obtaining constituent information of single-core molecules in the feedstock With reference to the flow chart in FIG. Step (1) for specifying the molecular structure of each component of (raw material oil) will be explained.
Step S1 (mass spectrometry) (S1 in FIG. 2)
Step 1 is a step of performing FT-ICR MS on a multi-component mixture, identifying the molecular formulas of the molecules assigned to each of the obtained peaks, and further identifying the abundance ratio of the molecules. That is, a step of performing FT-ICR MS on heavy oil, identifying the molecular formula of the molecule assigned to each peak for all the peaks obtained thereby, and further identifying the abundance ratio of the molecule corresponding to that molecular formula. is.

According to the FT-ICR-mass spectrometer, high-precision measurement can be performed by softly ionizing a sample to form molecular ions or pseudo-molecular ions.

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 of ionizing a molecule and colliding it with an inert gas such as argon to break crosslinks and side chains. Generally, it is preferred to provide collision energy such that cross-links and side chains in each component making up the multi-component mixture are broken. Fragment ions for each core are generated by cleaving the cross-links and side chains. This core may have, as a side chain, an aliphatic group having about 0 to 4 carbon atoms that could not be cleaved by collision-induced dissociation.

When FT-ICR-MS is performed on a multicomponent mixture, it is possible to determine the molecular formulas of the molecules that make up the multicomponent mixture from the m/z values of the peaks obtained. I can't get it. Therefore, if collision-induced dissociation is further performed to break the crosslinks and side chains in each molecule that constitutes the multicomponent mixture, the types of cores present in the entire multicomponent mixture can be known.

The conditions for collision-induced dissociation are preferably collision energy capable of effectively severing crosslinks and side chains in the molecule, for example, 10 to 50 kcal/mol, more preferably 20 to 40 kcal/mol. 40 kcal/mol corresponds to 32 eV when the molecular weight is 700.

Step S3 (identification of structure and existence ratio of each core) (S3 in FIG. 2)
Step S3 is a step of performing FT-ICR-MS for each fragment ion generated by the collision-induced dissociation in step 2 to specify the structure and abundance ratio of cores constituting each fragment ion.

(a) First, a method for specifying the structure of the core that constitutes each fragment ion will be described.
Specifically, it is a method of collating the information about the cores obtained in step 2 with the information about the cores described in the core structure list prepared in advance to specify the structure of each core.
Details are as follows.
i. Acquisition of information on the core after collision-induced dissociation In FT-ICR-MS of each fragment ion after collision-induced dissociation, even if the core part is the same, aliphatic side chains with 0 to 4 carbon atoms Fragment ions having groups appear as separate peaks because they have different masses depending on the type of side chain.

Therefore, for a core having an aliphatic group having 0 to 4 carbon atoms as a side chain, the mass of each of these is calculated in advance, and the different peaks that appear are compared and collated in various ways, and the mass of the core itself can be assigned.

Using this method, in step 2, for each of the peaks obtained after collision-induced dissociation, the core attributed to that peak is how many masses and how many heteroatoms such as O, N or S atoms are present. , and information on how many aromatic rings are present can be obtained from the DBE value.

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

iii. Core structure list The types of cores to be stored in the above core structure list are not particularly limited and may be of any type. 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, which is a sample. For example, when the multi-component mixture is petroleum, a "core structure list for specifying the molecular structure of petroleum" may be prepared in advance based on the knowledge about petroleum so far and used.

In creating the list, the number of rings in the basic aromatic ring, the type and number of naphthenic rings directly bonded to the aromatic ring (including the difference between cata-type and peri-type), and the mode of direct bonding (that is, the basic aromatic ring It is preferable to store an appropriate number of cores in consideration of various conditions such as which position and in what form the naphthene ring is bonded.

For example, the size of the aromatic ring is up to 11 rings, and the heteroatom is assumed to be N, O, S, and the number of types of heterocycles is about 10, etc., considering convenience in calculation. Just make a list.

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

(b) Next, a method for specifying the existence ratio of each core will be described.
As described above, from the height of each peak obtained after collision-induced dissociation in step S2, the m/z, that is, the existence ratio of cores having that mass can be obtained.
The structure and existence ratio of each core after collision-induced dissociation obtained in step S3 are used in step S4.

Step S4 (Estimation of existence mode and existence ratio of cores 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” , is the step of estimating the mode of existence and the proportion of existence thereof.
In other words, the molecules belonging to all the peaks in step S1 are classified into “classes” based on “type and number of heteroatoms (including zero) and DBE value” in each molecular formula specified in step S1. It is a step of dividing and estimating the mode of existence and the proportion of all molecules belonging to each of the "classes".

The step S4 will be described in detail below.
(a) In step S1, the molecular formulas are identified for all peaks, so the type and number of heteroatoms in the molecular formula and the DBE value are known. Therefore, in this step, each of the molecules attributed to all peaks is grouped by "type, number, and DBE value of heteroatom" based on the "type, number, and DBE value of heteroatom." into each "class".

"Types and numbers of heteroatoms" are, in detail, "types of heteroatoms and the number of heteroatoms for each type". A heteroatom is preferably a nitrogen atom, a sulfur atom, or an oxygen atom, so the "type and number of heteroatoms" preferably means "the number of nitrogen atoms, sulfur atoms, and oxygen atoms". can also Therefore, with respect to heteroatoms, "those having the same number of nitrogen atoms, sulfur atoms and oxygen atoms all matching" belong to the same "class".

(b) Next, in each class bounded by the "kind and number of heteroatoms and DBE value" described in (a), each molecule belonging to that class is estimated to be a single core. Here, even if it is a multi-core, it is divided into those single cores, and the proportion of each single core is estimated.

In performing these estimations, it is preferable to make some assumptions for practical calculation convenience. Here, "multi-core" can be combined in various ways depending on what kind of cores are crosslinked and bonded. However, in this model, the multi-core is divided into the single cores that constitute it, and the ratio of the single cores is estimated. For example, when there is a double core (single core-crosslinking-single core), this model divides it into single cores and considers them all to exist as single cores. More specifically, a double core (single-core (4-ring)-bridged-single-core (5-ring)) is a double-core with a total number of rings of 9, and there are single-core (4-ring) and single-core (5-ring). Consider.

(c) As described above, the molecules belonging to each of the peaks obtained by FT-ICR-MS are reclassified into classes having the same type and number of heteroatoms and the same DBE value. Then, the type and number of heteroatoms and the DBE value of the single core belonging to that class are used as indexes to estimate what kind of core the single core is composed of.

(d) Next, estimate "in what ratio are the single cores, which are molecules belonging to that class, respectively?"
The existence ratio of each single core is assumed to be the sum of the existence ratios with respect to the total number of rings, and this is used as an estimated value. As described above, in the method of the present invention, constituent information about single-core molecules, in particular, the abundance of single-core molecules, the total number of rings, the number of aromatic rings, and the number of naphthenic rings are used as indicators for estimating the amount of coke produced. becomes. Therefore, according to a preferred embodiment of the present invention, in step (1), the amount of single-core molecules present in the feedstock oil is estimated as the component information of each single-core molecule in the feedstock oil. Also, according to a more preferred aspect of the present invention, in step (1), each component of the feedstock is ramped based on structural factors including the total number of rings, the number of aromatic rings and the number of naphthenic rings.

Through the steps S1 to S4 described above, it is possible to specify the required molecular structure by JACD for each component constituting the multi-component mixture, and to specify the abundance ratio thereof.

In steps S1 to S4, the physical property values of each component may be obtained from the molecular structure of each component of the multi-component mixture specified using JACD. Such physical property values can be used to predict the properties of the produced oil in addition to the amount of coke produced. These physical property values are preferably specified for the molecular structure of each component of the multi-component mixture specified as described above using the complete petroleum molecule database (Comcat).

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

Step (2): Constituent information of a single-core molecule having a total number of rings of 4 or more and a naphthene ring number of 2 or more and a single-core molecule having a total number of rings of 7 or more and a naphthene ring number of 1 or less According to one embodiment of the present invention, a single-core molecule having a total ring number of 4 or more and a naphthene ring number of 2 or more and a total ring number of 7 or more and The amount of coke produced is calculated using the ratio or amount of single-core molecules having one or less naphthenic rings as an index. The ratio or amount of specific single-core molecules in the raw material oil as described above can be correlated with the amount of coke produced, and thus can be advantageously used in estimating the amount of coke produced with high accuracy.

In addition, as shown in the examples described later, a single-core molecule having a total number of rings of 7 or more has a particularly high conversion rate to coke, and is therefore preferable as an index for calculating the amount of coke produced. Therefore, according to a preferred embodiment of the present invention, in step (2), a single-core molecule having a total number of rings of 4 or more and a naphthenic ring number of 2 or more and a single-core molecule having a total number of rings of 7 or more and a naphthenic ring number of 7 or more We assume that any single-core molecule for which is less than or equal to 1 is converted to coke.

The correlation between the above single-core molecules in the raw material oil and the amount of coke produced depends on the raw material oil (type, property, etc.) and the reaction conditions (reaction temperature, catalyst type, catalyst/oil ratio, etc.) in fluid catalytic cracking equipment. can change from time to time. Therefore, according to one embodiment of the present invention, in step (2), it is preferable to calculate the amount of coke produced using a regression coefficient or a correlation curve preset for each feed oil and its reaction conditions.

According to one embodiment of the present invention, the feedstock may be either light oil or heavy fraction, preferably heavy fraction. More specifically, the raw material oil includes desulfurized heavy oil such as desulfurized atmospheric residue (DSAR) and desulfurized vacuum gas oil (DSVGO), preferably desulfurized atmospheric residue (DSAR), desulfurized vacuum light oil (DSVGO) or a combination thereof.

According to one embodiment of the present invention, the density of the feedstock is not particularly limited, but is preferably 0.8 to 1.0, more preferably 0.85 to 0.97, and even more preferably 0.88 to 0.95.

According to one embodiment of the present invention, the residual carbon content in the feedstock is preferably 0.1 to 6.0% by mass, more preferably 1.0 to 6.0% by mass, and even more preferably is 2.0 to 6.0% by mass.

According to one embodiment of the present invention, the type of catalyst defined for the above reaction conditions is not particularly limited and includes, but is not limited to, vanadium, nickel, zinc, iron or cobalt and the like. From the viewpoint of efficient fluid catalytic cracking reaction, vanadium, zinc, nickel, iron or cobalt-supported catalysts (JP-A-2003-27065, etc.), vanadium metal in the pores of the molecular sieve cationic species (Patent No. 3545652, etc.), and furthermore, a catalyst containing zeolite in which rare earth elements such as lanthanum and cerium are introduced into the pores of the molecular sieve together with vanadium metal (Patent No. 3550065 publications, etc.) may be used.

According to one embodiment of the present invention, the catalyst/oil ratio in the fluid catalytic cracking apparatus is not particularly limited, but from the viewpoint of efficient implementation of the fluid catalytic cracking reaction, it is preferably 4 to 9, and more It is preferably 4 to 8, and even more preferably 5 to 7.5.

According to one embodiment of the present invention, the reaction temperature in the fluid catalytic cracking apparatus is not particularly limited, but from the viewpoint of efficient implementation of the fluid catalytic cracking reaction, it is preferably 480 to 560 ° C., more preferably is 500-550°C, more preferably 520-540°C.

The above estimation method of the present invention can be used in adjusting the operating conditions of fluid catalytic cracking units from the viewpoint of improving the profitability of refineries. Therefore, according to a preferred embodiment, there is provided a method for operating a fluid catalytic cracking unit, wherein the operating conditions of the fluid catalytic cracking unit are set based on the estimated coke production amount obtained by the above method of the present invention.

<Equipment and system for estimating the amount of coke produced in fluidized catalytic cracking equipment>
Next, with reference to FIG. 3, one embodiment of the coke production amount estimating device in the fluidized catalytic cracking apparatus of the present invention will be described. FIG. 3 is a functional block diagram of a device for estimating the amount of coke produced in fluidized catalytic cracking equipment. In FIG. 3, illustration of an interface for inputting and outputting information is omitted.

In FIG. 3, the coke production amount estimation device 1 in fluid catalytic cracking equipment is
(1) A raw oil analysis unit 10 that obtains constituent information of single core molecules in the raw oil based on the results of raw oil analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS),
(2) based on the constituent information of a single-core molecule having a total number of rings of 4 or more and a naphthene ring number of 2 or more and a single-core molecule having a total number of rings of 7 or more and a naphthene ring number of 1 or less; , a coke production amount calculator 20 for calculating the coke production amount
Prepare.

The raw oil analysis unit 10 can be composed of an ionization unit 11 and a component information analysis unit 12 . The ionization unit 11 may be equipped with one or more ionization devices so that types such as the APPI method, Ag-ESI method, LDI method, and Ag-LDI method can be selected. Nebulizer), vaporizer, lamp (UV lamp, etc.) may be provided, and may be connected to the mass spectrometer in the main body of the FT-ICR-MS via a capillary or the like.

In addition, the component information analysis unit 12 can be composed of an FT-ICR-MS, a storage unit in which information about petroleum components is stored as a database, and a calculation unit. Based on the information of each component obtained and the information stored in the storage unit, the composition information of each component can be analyzed in the calculation unit. The computing unit and the storage unit include, for example, a database and a program (JACD (Juxtaposed Attributes for Chemical-structure Description) described in JP-A-2014-218643 and JP-A-2020-502495 by the present applicant). etc.) are stored and an analysis of the constituent information of the feedstock including the structure and abundance of the core molecule, the side chains of the core molecule and the aliphatic molecules is performed.

The coke production amount calculation unit 20 calculates the coke production amount from the component information of the raw oil obtained from the component information analysis unit 12 . The coke production amount calculation unit 2 may be composed of a storage unit in which necessary information is stored as a database, and a calculation unit that calculates the coke production amount based on the above information.

According to one embodiment of the present invention, a single-core molecule having a total number of rings of 4 or more and a naphthene ring number of 2 or more and a single-core molecule having a total number of rings of 7 or more and a naphthene ring number in the coke production amount calculation unit 20 is 1 or less, the amount of coke produced is calculated using the ratio or amount of single-core molecules present as an index. According to a preferred embodiment of the present invention, in the coke production amount calculator 20, a single-core molecule having a total ring number of 4 or more and a naphthene ring number of 2 or more and a total ring number of Any single-core molecule with 7 or more and 1 or less naphthenic rings is assumed to be converted to coke.

In the coke production amount calculator 20, it is preferable to record in advance the single core molecule and the regression coefficient or correlation curve relating to the coke production amount for each raw material oil and its reaction conditions. Such regression coefficients or correlation curves can be advantageously used in calculating the amount of coke produced based on the constituent information of the single core molecule, feed oil and reaction conditions.

The apparatus may be configured as a system in which multiple units are combined. Therefore, according to another aspect of the present invention, a system for estimating the amount of coke produced in fluid catalytic cracking units, comprising:
(1) a feedstock analysis unit that obtains information on the composition of single core molecules in the feedstock based on the results of feedstock analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS); Amount of coke produced based on component information of a single-core molecule having 4 or more rings and 2 or more naphthenic rings and a single-core molecule having 7 or more total rings and 1 or less naphthenic rings A system is provided that includes a coke production amount calculator that calculates the

In the present invention, a series of processes for estimating the amount of coke produced can be executed by hardware, software, or a combination of these. When executing processing by software, install the program recording the processing sequence in the memory within the computer built into the dedicated hardware and execute it, or install the program in a general-purpose computer capable of executing various processing. can be executed by

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

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

The method of the present invention can be preferably implemented by a computer storing the above computer program in an internal storage device.

In addition, the various processes described in this specification are not only executed in chronological order according to the description, but may also be executed in parallel or individually according to the processing capacity of the device that executes the process or as necessary. . Further, in this specification, a system is a logical collective configuration of a plurality of devices, and is not limited to one in which the devices of each configuration are in the same housing.
Although the embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the present invention.

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

Test Example 1: Decomposition test of DSAR by RFCC equipment (1) Preparation of RFCC equipment and samples A plurality of feedstock oils containing DSAR, DSVGO, and a mixture thereof were treated with an RFCC bench equipment, and the resulting product oil was treated at normal pressure. Fractionation was performed under distillation conditions, and the correlation with the feedstock composition was analyzed. Table 2 shows some of the feedstocks.

Next, using the RFCC bench apparatus (fluidized bed type) shown in the schematic diagram of FIG. 4, a fluidized catalytic cracking test of feed oil was carried out.

First, a predetermined amount of catalyst was set in the regeneration tower, then the system was pressurized with nitrogen gas and the regeneration tower was pressurized with air to establish catalyst circulation. The inside of the system was raised to a predetermined reaction temperature, and the temperature of the regeneration tower was raised to the catalyst regeneration temperature. After reaching the target temperature, a predetermined amount of feed oil was sprayed. The recovery of the produced oil was started when the catalyst circulation amount stabilized at a predetermined catalyst/oil ratio (C/O). The product is subjected to gas-liquid separation in a fractionator, and the liquid component is recovered from the receiver. The catalyst continued to circulate and react while regenerating the catalyst in the regeneration tower, and the test was continued until a predetermined amount of the produced oil-liquid component was recovered. Exhaust gas generated in the catalyst regeneration process is discharged from the regeneration tower.

The test was conducted under a plurality of reaction conditions including those shown in Table 3, and the amount of coke produced was measured. The amount of coke produced was calculated from the results of measuring carbon dioxide in the exhaust gas discharged from the regeneration tower.

In addition, the components of the raw material oil were identified using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). In the FT-ICR-MS measurement, both a mode for observing parent ions (ParentIon) and a mode for observing daughter ions (DaugHTEr Ion) were used and converted into JACD codes.

Here, the compounds in the raw material oil are lined into four types of structural factors: "core structure", "crosslinked structure", "side chain structure" and "aliphatic". Also, in this model, all core structures are classified as single cores. For example, a double core molecule (4-ring + bridge + 5-ring structure) has a total of 9 rings, but is considered to have a single-core molecule (4-ring) and a single-core molecule (5-ring).

Next, we analyzed the correlation between the structure factor (core) and the amount of coke produced for each of multiple feedstock oils with different reaction conditions (reaction temperature, catalyst/oil ratio, etc.) and general properties (residual carbon content, distillation fraction). .

As a result of the analysis, it was confirmed that the amount of single-core molecules having a total number of rings of 4 or more in the feedstock showed a correlation with the amount of coke produced. Some of the results are shown in FIG. In FIG. 5, the horizontal axis shows the measured value of the amount of coke produced (Coke amount (actual measurement), wt%), and the vertical axis shows the difference between the amount of cores in the feed oil and the amount of cores in the produced oil (reduction of cores from the feedstock). , wt %).

In FIG. 5, in the case of feedstocks (DSVGO, DSAR and DSVGO+DSAR (=3+7)) treated under the reaction conditions of a reaction temperature of 520°C and a catalyst/oil ratio (C/O) of 5, the total number of rings in the feedstock is A correlation was shown between the amount of core reduction in a single-core molecule with 4 or more rings (Core 4-ring+) or a single-core molecule with a total number of rings of 5 or more (Core 5-ring+) and the amount of coke produced. It can be seen that in DSVGO, the amount of decrease in single-core molecules with a total number of rings of 4 or more is balanced with the amount of coke produced.

Furthermore, the relationship between the total number of rings and the number of naphthene rings in the raw material oil and the presence or absence of coke formation was analyzed, and the results were as shown in Table 4.
Single-core molecules having a total number of rings of 4 or more and a naphthenic ring number of 2 or more and single-core molecules having a total number of rings of 7 or more and a naphthenic ring number of 1 or less all produced coke. was

Based on the above results, the total number of ring Estimate the amount of coke produced based on the amount of single-core molecules having a number of 4 or more and 2 or more naphthenic rings and single-core molecules having a total number of rings of 7 or more and 1 or less naphthenic rings, It was compared with the measured value.

Table 5 shows the results for the feedstock treated under the reaction conditions of a reaction temperature of 520°C and a catalyst/oil ratio (C/O) of 5. The estimated amount of coke produced and the measured value were almost in agreement.

From the above results, constituent information of a single-core molecule having a total ring number of 4 or more and a naphthene ring number of 2 or more and a single-core molecule having a total ring number of 7 or more and a naphthene ring number of 1 or less and the amount of coke produced, and it was confirmed that the amount of coke produced from the feed oil can be estimated by preparing a regression line in advance.

According to the present invention, the amount of coke produced in a fluid catalytic cracking unit can be estimated with high accuracy by combining information on the constituent components of the single-core molecules of feedstock obtained by FT-ICR MS. Accurately estimating the amount of coke produced in fluidized catalytic cracking units contributes to dramatically improving the operational stability and operational efficiency of petroleum refining facilities.

1 Coke production amount estimation device in fluid catalytic cracking equipment 10 Raw material oil analysis unit 11 Ionization unit 12 Component information analysis unit 20 Coke production amount calculation unit

Claims (17)

A method for estimating the amount of coke produced in a fluidized catalytic cracking unit by a computer,
(1) obtaining constituent information of single core molecules in the feedstock based on the results of feedstock analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS); The amount of coke produced is calculated based on the component information of the single-core molecule having 4 or more and 2 or more naphthenic rings and the single-core molecule having 7 or more total rings and 1 or less naphthenic rings. a method comprising the step of 2. The process of claim 1, wherein said fluid catalytic cracking units are fluid catalytic cracking (FCC) units or residual oil fluid catalytic cracking (RFCC) units. 3. The method according to claim 1 or 2, wherein the constituent information of the single-core molecule in the feedstock in step (1) includes the abundance or abundance of the single-core molecule in the feedstock. 4. The method according to any one of claims 1 to 3, wherein step (1) comprises ramping the single core molecules in the feedstock based on structural factors including total ring number, aromatic ring number and naphthenic ring number. The method described in section. The method according to any one of claims 1 to 4, wherein step (2) includes calculating the amount of coke produced using a regression coefficient preset for each feed oil and its reaction conditions. In step (2), a single-core molecule having a total number of rings of 4 or more and a naphthene ring number of 2 or more and a single-core molecule having a total number of rings of 7 or more and a naphthene ring number of 1 or less are treated with coke A method according to any one of claims 1 to 5, presuming that it is converted to The method according to any one of claims 1 to 6, wherein the feedstock has a density of 0.8 to 1.0. The method according to any one of claims 1 to 7, wherein the residual carbon content in the feedstock is 0.1 to 6.0% by weight. The method according to any one of claims 1 to 8, wherein said feedstock is a light fraction or a heavy fraction. Process according to any one of the preceding claims, wherein the reaction temperature of the fluid catalytic cracking units is 480-560°C. A process according to any preceding claim, wherein the catalyst/oil ratio in the fluid catalytic cracking units is 4-9. A method for operating a fluid catalytic cracking unit, wherein operating conditions are set based on an estimated coke production amount obtained by the method according to any one of claims 1 to 11. A device for estimating the amount of coke produced in a fluidized catalytic cracking unit,
(1) a feedstock analysis unit that obtains information on the composition of single core molecules in the feedstock based on the results of feedstock analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS); Coke generation based on the component information of a single-core molecule having 4 or more rings and 2 or more naphthenic rings and a single-core molecule having 7 or more total rings and 1 or less naphthenic rings An apparatus comprising a coke production amount calculator for calculating an amount. A system for estimating the amount of coke produced in fluid catalytic cracking equipment,
(1) a feedstock analysis unit that obtains information on the composition of single core molecules in the feedstock based on the results of feedstock analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS); Coke generation based on the component information of a single-core molecule having 4 or more rings and 2 or more naphthenic rings and a single-core molecule having 7 or more total rings and 1 or less naphthenic rings A system including a coke production amount calculator for calculating the amount. A computer program for carrying out the method according to any one of claims 1 to 11, the apparatus according to claim 13 or the system according to claim 14. A recording medium recording the computer program according to claim 15 . A computer storing the computer program according to claim 15 in an internal storage device.

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