JP7746042B2 - Information processing method, cracked light oil yield calculation device, cracked light oil yield calculation program, and non-transitory computer readable recording medium - Google Patents

Description

The present invention relates to an information processing method, a cracked light oil yield calculation device, a cracked light oil yield calculation program, and a non-transitory computer-readable recording medium.

Atmospheric residue, obtained by atmospheric distillation of crude oil, contains high concentrations of sulfur. The method of reducing the sulfur content of atmospheric residue by hydrotreating it is known as direct desulfurization.

During the hydrotreating of atmospheric residue, coke is produced as a by-product, and as this coke accumulates on the hydrotreating catalyst, the activity of the hydrotreating catalyst decreases over time. Atmospheric residue also contains metal compounds such as nickel and vanadium compounds, and these compounds accumulate as metals on the hydrotreating catalyst, causing the activity of the hydrotreating catalyst to decrease over time. Therefore, in order to keep the sulfur content in the resulting oil below a certain level, the reaction temperature must be increased during operation to counteract the decrease in activity of the hydrotreating catalyst.

On the other hand, during the hydrotreating of atmospheric distillation residue, light fractions including naphtha, kerosene, and diesel (hereinafter abbreviated as "cracked light oil") are produced as by-products, so production management must be carried out to balance this cracked light oil with the residual heavy oil. The amount of cracked light oil obtained fluctuates over time depending on the cracking activity of the hydrotreating catalyst, the reaction temperature, etc.

Changes in the product supply and demand environment may result in an increase in the supply of cracked light oil. Accordingly, in atmospheric residue hydrotreating units, the amount of cracked light oil obtained must be significantly altered depending on the supply and demand situation. Therefore, a method for accurately estimating the amount of cracked light oil obtained is desired.

In the field of crude oil refining, various methods for accurately estimating various conditions have been studied. For example, Patent Document 1 discloses a method for estimating the reaction temperature required after switching to a feedstock containing atmospheric distillation light oil with different properties in the hydroprocessing of the feedstock containing atmospheric distillation light oil, based on information about the properties of the atmospheric distillation light oil before the switch and the operating conditions, and information about the properties of the atmospheric distillation light oil after the switch and the operating conditions other than the reaction temperature.

Japanese Patent Application Publication No. 10-60455

However, there is currently no method for estimating the yield of light cracked oil, and the current method is to use actual data from past operations.

The present invention has been made in consideration of the above circumstances, and aims to provide an information processing method capable of estimating the yield of cracked light oil under specified reaction conditions for the hydrotreating reaction of feedstock oil containing atmospheric distillation residue, a cracked light oil yield calculation device capable of estimating the yield of cracked light oil, a cracked light oil yield calculation program for causing a computer to function as the cracked light oil yield calculation device, and a non-transitory computer-readable recording medium storing the program.

In order to solve the above problems, the present invention has the following aspects.
[1] An information processing method for a hydrotreating reaction of a feedstock containing atmospheric distillation residue, comprising: an information acquisition step of acquiring information about the feedstock, information about the product oil, and information about operating conditions at a predetermined time after the start of the reaction; a degradation degree calculation step of calculating the degradation degree of a desulfurization reaction and the degradation degree of a cracking reaction of a catalyst using a degradation function based on the acquired information about the feedstock, information about the product oil, and information about the operating conditions; a reaction temperature calculation step of calculating the information about the feedstock, information about the product oil, and the reaction temperature required to satisfy the operating conditions based on the degradation degree of the desulfurization reaction of the catalyst; and a cracked light oil yield calculation step of calculating the yield of cracked light oil based on the reaction temperature and the degradation degree of the cracking reaction of the catalyst.
[2] The information processing method according to [1], wherein the deterioration function is composed of a coke deterioration function relating to catalyst deterioration due to coke deposition and a metal deterioration function relating to catalyst deterioration due to metal deposition.
[3] The information processing method according to [1] or [2], wherein the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil, and the information about the product oil includes information about the sulfur concentration in the product oil.
[4] The information processing method according to any one of [1] to [3], wherein the information about the operating conditions includes information about hydrogen partial pressure, information about catalyst loading, and information about the feedstock supply amount.
[5] A cracked light oil yield calculation device including: an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions at a predetermined time after the start of the hydrotreating reaction of a feedstock containing atmospheric distillation residue; and a calculation unit that calculates the degree of degradation of the desulfurization reaction and the degree of degradation of the cracking reaction of the catalyst using a degradation function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates the information about the feedstock, information about the product oil, and the reaction temperature required to satisfy the operating conditions based on the calculated degree of degradation of the desulfurization reaction of the catalyst, and calculates the amount of cracked light oil yield based on the calculated reaction temperature and the degree of degradation of the cracking reaction of the catalyst.
[6] The light cracked oil yield calculation device according to [5], wherein the deterioration function is composed of a coke deterioration function relating to catalyst deterioration due to coke deposition and a metal deterioration function relating to catalyst deterioration due to metal deposition.
[7] The information about the feedstock oil includes information about the sulfur concentration in the feedstock oil, and the information about the product oil includes information about the sulfur concentration in the product oil. [5] or [6] The cracked light oil yield calculation device according to [6].
[8] The cracked light oil yield calculation device according to any one of [5] to [7], wherein the information on the operating conditions includes information on hydrogen partial pressure, information on catalyst loading amount, and information on the feedstock oil supply amount.
[9] A cracked light oil yield calculation program for causing a computer to function as the cracked light oil yield calculation device according to any one of [5] to [8].
[10] A non-transitory computer-readable recording medium storing the program according to [9].

The present invention provides an information processing method capable of calculating the yield of cracked light oil under specified reaction conditions for the hydrotreating reaction of feedstock oil containing atmospheric distillation residue, a cracked light oil yield calculation device capable of calculating the yield of cracked light oil, a cracked light oil yield calculation program for causing a computer to function as the cracked light oil yield calculation device, and a non-transitory computer-readable recording medium storing the program.

1 is a flowchart of an information processing method according to an embodiment. 1 is a block diagram showing the configuration of a cracked light oil yield calculation device according to an embodiment.

The following describes in detail the embodiments of the present invention. However, the following description is merely an example of an embodiment of the present invention, and the present invention is not limited to these details and can be modified and implemented within the scope of its essence.

<Information processing method>
The information processing method of this embodiment relates to a hydrotreating reaction of a feedstock containing atmospheric distillation residue oil. The method includes an information acquisition step (S1 in FIG. 1) for acquiring information about the feedstock, the product oil, and the operating conditions at a predetermined time after the reaction has started, and a degradation calculation step (S2 in FIG. 1) for calculating the degradation level of the catalyst desulfurization reaction and the degradation level of the cracking reaction using a degradation function based on the acquired information about the feedstock, the product oil, and the operating conditions. The method also includes a reaction temperature calculation step (S3 in FIG. 1) for calculating the reaction temperature required to satisfy the feedstock, the product oil, and the operating conditions based on the degradation level of the catalyst desulfurization reaction. The method also includes a cracked light oil yield calculation step (S4 in FIG. 1) for calculating the yield of the cracked light oil based on the reaction temperature and the degradation level of the cracking reaction of the catalyst. Each step will be described below. The following steps are executed, for example, by the cracked light oil yield calculation device 1 of this embodiment. For example, S1 is executed by the acquisition unit 11, and S2, S3, and S4 are executed by the calculation unit 13 in the computer main body 12.

<Information Acquisition Steps>
The information acquisition step of this embodiment is a step of acquiring information about the feedstock oil, information about the product oil, and information about the operating conditions when a predetermined time has elapsed since the start of the reaction. The predetermined time after the start of the reaction refers to, for example, any t days having elapsed since the start of the reaction. t may be an integer or a decimal; for example, if t is 0.5, it means that 12 hours have elapsed since the start of the reaction. Furthermore, the time when t days have elapsed may be in the past, present, or future from the time when the information processing method of this embodiment is implemented. For example, if the information processing method of this embodiment is implemented two days after the start of the reaction and t is 4, the reaction temperature two days later (in the future) will be estimated.

(Information about feedstock oil)
Examples of the information about the feedstock include information about the composition of the feedstock, such as information about the sulfur concentration and metal concentration in the feedstock.

Information regarding the sulfur concentration in the feedstock oil can be obtained using sulfur concentration measurement methods known in the art, such as ultraviolet fluorescence spectroscopy and wavelength-dispersive X-ray fluorescence spectroscopy. The sulfur concentration in the feedstock oil can also be controlled by changing the feedstock oil. It is preferable that the information regarding the sulfur concentration in the feedstock oil is a set value. In other words, the sulfur concentration of the feedstock oil planned for use can be used.

Information regarding the metal concentration in the feedstock can be obtained using metal concentration measurement methods known in the art, such as ICP-MS and X-ray fluorescence analysis. The metal concentration in the feedstock can also be controlled by changing the feedstock. It is preferable that the information regarding the metal concentration in the feedstock is a set value. In other words, the metal concentration of the feedstock planned for use can be used.

(Information about produced oil)
Examples of the information about the product oil include information about the composition of the product oil, such as information about the sulfur concentration and metal concentration in the product oil.

Information regarding the sulfur concentration in the product oil can be obtained in the same manner as in the case of the feedstock oil described above. In this embodiment, the information regarding the sulfur concentration in the product oil is preferably a set value. In other words, the sulfur concentration of the target product oil can be used.

Information regarding the metal concentration in the product oil can be obtained in the same way as in the case of the feed oil described above. In this embodiment, the information regarding the metal concentration in the product oil is preferably a set value. In other words, the metal concentration of the target product oil can be used. Note that if the sulfur concentration in the product oil described above is constant, the metal concentration in the product oil will also be constant.

(Information about operating conditions)
Examples of information about operating conditions include information about hydrogen partial pressure, information about catalyst loading, feedstock feed rate, and information about hydrogen feed rate. For example, the information about operating conditions is at least one of information about hydrogen partial pressure, information about catalyst loading, information about feedstock feed rate, and information about hydrogen feed rate. In particular, the information about operating conditions preferably includes information about hydrogen partial pressure, information about catalyst loading, and information about feedstock feed rate, and more preferably includes all of information about hydrogen partial pressure, information about catalyst loading, information about feedstock feed rate, and information about hydrogen feed rate. The operating conditions also include time information, such as an arbitrary t days after the start of the reaction. The operating conditions also include information about the actual measured value of the reaction temperature. The operating conditions may also include information about the actual measured yield of cracked light oil.

Information regarding hydrogen partial pressure, catalyst loading, feedstock feed rate, and hydrogen feed rate can be determined by methods known in the art. Information regarding hydrogen partial pressure, catalyst loading, feedstock feed rate, and hydrogen feed rate can be controlled in the hydrotreating reaction of feedstocks, including atmospheric residue. Information regarding operating conditions is preferably a set value; that is, the intended operating conditions are used.

<Deterioration level calculation step>
The deterioration degree calculation step in this embodiment is a step of calculating the deterioration degree of the desulfurization reaction and the deterioration degree of the cracking reaction of the catalyst using a deterioration function based on the acquired information about the feedstock oil, information about the product oil, and information about the operating conditions.
The step of calculating the degradation degree of the desulfurization reaction will be described below. The step of calculating the degradation degree of the decomposition reaction will be described later.

<Deterioration of desulfurization reaction>
The deterioration degree of the desulfurization reaction is expressed by the following formula 1.
Φ=k _t /k ₀ Equation 1
In the above formula 1, _k0 is the reaction rate constant of the desulfurization reaction of the catalyst after 0 days of reaction (i.e., at the start of the reaction), and _kt is the reaction rate constant of the desulfurization reaction of the catalyst after t days of reaction. Note that _k0 and _kt are reaction rate constants of the desulfurization reaction at a temperature T _SOR described below.

In this embodiment, the degree of degradation of the catalyst's desulfurization reaction can be calculated using the desulfurization reaction degradation function based on the acquired information about the feedstock oil, information about the product oil, and information about the operating conditions.

<Degradation function of desulfurization reaction>
The desulfurization reaction deterioration function is a function for calculating the degree of deterioration of the desulfurization reaction of the catalyst. In this embodiment, the desulfurization reaction deterioration function is preferably composed of a coke deterioration function relating to the deterioration of the desulfurization reaction of the catalyst due to coke deposition, and a metal deterioration function relating to the deterioration of the desulfurization reaction of the catalyst due to metal deposition. Such a desulfurization reaction deterioration function is not particularly limited, but an example thereof is the desulfurization reaction deterioration function expressed by the following equation 2:

Φ = Φ _C Φ _M Equation 2
In the above equation 2, Φ _C is the coke depletion function, and Φ _M is the metal depletion function.

Below, we will explain the coke degradation function and the metal degradation function.

<Coke Deterioration Function 1>
The coke deterioration function is not particularly limited as long as it is a function that can calculate the degree of deterioration of the desulfurization reaction related to coke deterioration of the catalyst. For example, coke deterioration function 1 expressed by the following formula 3 can be given as an example.

Φ _C =exp(-Dt) Equation 3
In the above formula 3, D is the deterioration coefficient of the active species of the desulfurization reaction of the catalyst due to coke, and t is the number of days elapsed since the reaction began.

D can be calculated using Equation 4 below. Equation 4 below is an equation that can calculate the deterioration coefficient due to coke, an active species in the desulfurization reaction of a catalyst, using specific parameters. It was first discovered by the inventors of this application based on the operating results of an actual plant.

In the above formula 4, α is the catalyst constant of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst), S _F is the sulfur concentration (mass%) in the feedstock oil after t days of reaction, S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, LHSV is the liquid hourly space velocity (h ^-1 ) after t days of reaction, P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is a gas constant: 0.00831 (kJ / (mol · K)), T _B is the reference reaction temperature (K), and T _SOR is the required temperature on day 0 (K).

As used herein, the term "required temperature" refers to the reaction temperature required to achieve predetermined reaction conditions. That is, the required temperature on day 0 refers to the reaction temperature required to achieve the above-mentioned reaction conditions of S _F , S _P , LHSV, and P at the start of the reaction.

In this specification, "reference hydrogen partial pressure" refers to the standard pressure under actual reaction conditions. It is calculated as the average reaction pressure used when determining the hydrogen partial pressure coefficient a, which will be described later.

In this specification, the "reference reaction temperature" means the average value of T _SOR obtained over a range of standard operating conditions that may be actually encountered during operation.

In Equation 4, T _SOR represents the initial activity of the desulfurization reaction of the catalyst, and α represents the deterioration rate of the desulfurization reaction of the catalyst. That is, the larger the values of T _SOR and α, the greater the deterioration of the desulfurization reaction of the catalyst, and this deterioration behavior is reflected in the value of D.

In the above equation 4, the term expressed by (1/S _P ^n-1 -1/S _F ^n-1 )LHSV is a desulfurization reaction rate constant, and as described above, is a constant when S _P , S _F , and LHSV are set values and operation is performed under constant conditions. In the above equation 4, the term expressed by (P _B /P) ^a is a term indicating hydrogen partial pressure dependency, and as described above, is a constant when P is set value and operation is performed under constant conditions. In the above equation 4, the term expressed by exp[Ec/R(1/T _B -1/T _SOR )] is a term indicating temperature dependency and is a constant.

In the above formula 4, S _F , S _P , LHSV, and P are values substituted based on the information on the feed oil, the information on the product oil, and the information on the operating conditions acquired in the above-mentioned information acquisition step. Note that LHSV can be calculated by dividing the feed oil supply rate (volume/h) by the catalyst loading amount (volume).

As described above, S _F , LHSV, and P are controllable parameters. Furthermore, S _P is the sulfur concentration of the target product oil. That is, the deterioration coefficient due to coke, an active species in the desulfurization reaction of the catalyst, can be calculated using Equation 4 under the reaction conditions of S _F , S _P , LHSV, and P. The method for determining n, which is the reaction order of the hydrotreating reaction of feedstock oil containing atmospheric distillation residue, will be described later.

(How to determine basic coke deterioration parameters)
In the above formula 4, α, P _B , a, Ec, T _B , and T _SOR are constants. Hereinafter, these parameters will be collectively referred to as "basic coke deterioration parameter 1." The basic coke deterioration parameter 1 is a parameter determined depending on the catalyst used, and may be determined while performing a reaction in an actual reactor, or may be determined in advance on a bench scale based on the operating conditions of the actual reactor. In this embodiment, it is preferable to determine the parameter in advance on a bench scale based on the operating conditions of the actual reactor.
Below, examples of how to determine the basic coke deterioration parameters P _B , a, Ec, and T _B are shown. These methods (methods for determining P _{B , a, Ec, and T B} ) are based on the deterioration behavior of the catalyst desulfurization reaction (changes in the reaction rate constant of the desulfurization reaction) analyzed from data obtained from the above-mentioned reaction on an actual plant or a bench-scale reaction under actual _plant operating conditions. Two examples of how to determine α and T _SOR are shown, but the present invention is not limited to these. The first example is a method (method 1 for determining α and T SOR) in which the parameters are determined from the deterioration behavior of the catalyst desulfurization reaction (changes in the reaction rate constant of the desulfurization reaction) analyzed from data obtained from the above-mentioned reaction on an actual plant or a bench-scale reaction under actual plant operating conditions. The second example is a method (method 2 for determining α and T _SOR ) in which the parameters are determined from the reaction temperature profile analyzed from data obtained from the above-mentioned reaction on an actual plant or a bench-scale reaction under actual _plant operating conditions.

(How to calculate P _B , a, Ec, and T _B )
The method for determining the basic coke deterioration parameters in this embodiment is based on the deterioration behavior of the desulfurization reaction of the catalyst analyzed from data obtained from the above-mentioned reaction in an actual plant or a bench-scale reaction under actual plant operating conditions. The deterioration behavior (degree of deterioration) of the desulfurization reaction of this catalyst can be expressed by the following equation 5, based on the same concept as equation 1.
Φ'=k _t '/k ₀ ' Equation 5
In Equation 5, k ₀ ′ is the reaction rate constant of the desulfurization reaction of the catalyst after 0 days of reaction (i.e., at the start of the reaction), and k _t ′ is the reaction rate constant of the desulfurization reaction of the catalyst after t days of reaction. Note that k ₀ ′ and k _t ′ are reaction rate constants of the desulfurization reaction at a temperature T _SOR ′ described below.

Like Equation 1, Equation 5 is a degradation function based on the reaction rate constant of the desulfurization reaction. The reaction rate constant is expressed by the Arrhenius equation in Equation 6 below.

In the above formula 6, k is the reaction rate constant, A is the frequency factor, E is the activation energy (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), and T is the reaction temperature (K).

The reaction rate constant k ₀ ' of the desulfurization reaction at the reaction start temperature T _SOR ' decreases to k _t ' after t days of reaction. If the reaction temperature must be set to T _t ' to obtain activity equivalent to the reaction rate constant k ₀ ' of the desulfurization reaction after t days of reaction, the following formula 7 can be derived from formulas 5 and 6. Note that the reaction in this embodiment is a hydrotreating reaction of a feedstock oil containing atmospheric distillation residue, and therefore the activation energy E is the desulfurization activation energy Ea (kJ/mol).

In this embodiment, P _B , a, Ec, and T _B are calculated based on the above-mentioned formula 7.

(How to calculate Ec and T _B )
The reaction is carried out for a certain period of time under constant conditions of LHSV, hydrogen partial pressure, hydrogen/feed oil ratio, sulfur concentration in the feed oil, and metal concentration so that the sulfur concentration in the product oil becomes a certain value _SPn . Since the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature in order to make the sulfur concentration in the product oil _SPn . In this case, the metal concentration in the product oil also becomes constant. When the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis and a regression line is drawn, a straight line expressed as y = a _n x + b _n (0 < a _n ) is obtained. a _n and b _n are values reflecting the deterioration behavior of the catalyst. b _n in this straight line becomes T _SOR ' in the above-mentioned formula 7. In the above-mentioned formula 7, by substituting b _n for T _SOR ' and substituting the measured reaction temperature for T _t ', the deterioration degree Φ' of the desulfurization reaction after any reaction time t days has elapsed can be obtained. The activation energy Ea of desulfurization can be determined by the method described below. When the horizontal axis represents reaction time and the vertical axis represents the logarithm of Φ', a regression line is drawn, where y = -a _n 'x (|-a _n '| = a _n '). _{a n} ' represents the degradation rate of the desulfurization reaction of the catalyst.

The same reaction is carried out for n types of sulfur concentration S _Pn , and n a _n and b _n are determined in the same manner, and n a _n ' are obtained by the same method as above. n is an integer of 3 or more. The larger the number of n, the more accurate Ec can be obtained. On the other hand, if the number of n is too large, it takes a long time to obtain Ec, which is not efficient. In this embodiment, n is preferably 3 to 20, and more preferably 3 to 10.
The n a _n 's and b _n values thus obtained are respectively substituted into the following formula 8. The following formula 8 is an equation that can calculate the activation energy of coke and the reference reaction temperature, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

ln(a _n ')=ln(A)-(Ec/Rb _n ) Equation 8
In Equation 8, A is a frequency factor, Ec is the activation energy of coke deterioration (kJ/mol), and R is the gas constant: 0.00831 (kJ/(mol·K)).

For n combinations of a _n ' and b _n , ln(a _n ') is plotted on the vertical axis and 1/b _n on the horizontal axis, a regression line is drawn, and its slope is calculated. Since this slope is Ec/R, the activation energy Ec of coke deterioration can be calculated by subtracting R from the slope.

Also, T _B can be obtained by averaging n b _n values.

In determining Ec and _TB , it is preferable that the LHSV, hydrogen partial pressure, hydrogen/feed oil ratio, sulfur concentration in the feed oil, and metal concentration in the feed oil are conditions that correspond to the operating conditions of an actual plant.
Such an LHSV is, for example, 0.1 to 1.0 h ⁻¹ , the hydrogen partial pressure is, for example, 5 to 18 MPa, the hydrogen/feed oil ratio is, for example, 170 to 1400 [Nm ³ /kL], the sulfur concentration in the feed oil is, for example, 1 to 5 mass %, and the metal concentration in the feed oil is, for example, 10 to 200 mass ppm.
Similarly, it is preferable that the n-type sulfur concentrations S _Pn are set to conditions that correspond to the actual operating conditions of the engine, and such S _Pn is, for example, 0.5 mass % or less.
The reaction period is, for example, 100 to 500 days.

(How to calculate P _B and a)
The reaction is carried out for a certain period of time under the conditions of constant LHSV, hydrogen/feed oil ratio, sulfur concentration in the feed oil, metal concentration, and sulfur concentration in the product oil, and hydrogen partial pressure _Pm . Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature in order to maintain a constant sulfur concentration in the product oil. When the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis and a regression line is drawn, a straight line expressed as y = _amx + _bm (0 < _am ) is obtained. _bm on this line is T _SOR ' in the above-mentioned Equation 7. When _bm is substituted for T _SOR ' in the above-mentioned Equation 7 and the measured reaction temperature is substituted for _Tt ', the deterioration degree Φ' of the desulfurization reaction after any t days of reaction has elapsed can be obtained. When the reaction time is plotted on the horizontal axis and the logarithm of Φ' on the vertical axis and a regression line is drawn, a straight line expressed as y = -a _m'x (|-a _m '| = a _m ') is obtained. a _m ' represents the deterioration rate of the desulfurization reaction of the catalyst.

The same reaction is carried out for m types of hydrogen partial pressure P _m , m a _m and b _m are determined in the same manner, and m a _m ' are obtained by the same method as above. m is an integer of 3 or more. The larger the number of m, the more accurate a can be obtained. On the other hand, if the number of m is too large, it takes a long time to obtain a, which is not efficient. In this embodiment, m is preferably 3 to 20, and more preferably 3 to 10.
The m a _m 's and P _m obtained in this way are respectively substituted into the following formula 9. The following formula 9 is an equation that can calculate the hydrogen partial pressure coefficient and the reference hydrogen partial pressure, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

ln( _am ')=-aln( _Pm )+B1 Equation 9
In the formula 9, B1 can be 0.

For m combinations of a _m ' and P _m , ln(a _m ') is plotted on the vertical axis and ln(P _m ) on the horizontal axis, a regression line is drawn, and the slope is determined. This slope is the hydrogen partial pressure coefficient a.

Moreover, P _B can be obtained by averaging the m hydrogen partial pressures P _m .

In determining a and P _B , the LHSV, hydrogen/feed oil ratio, sulfur concentration in the feed oil, metal concentration in the feed oil, and sulfur concentration in the product oil are preferably set to conditions that correspond to the operating conditions of an actual plant.
Such an LHSV is, for example, 0.1 to 1.0 h ⁻¹ , the hydrogen/feedstock ratio is, for example, 170 to 1400 [Nm ³ /kL], the sulfur concentration in the feedstock is, for example, 1 to 5 mass %, the metal concentration in the feedstock is, for example, 10 to 200 mass ppm, and the sulfur concentration in the product oil is, for example, 0.5 mass % or less.
Similarly, it is preferable that the partial pressure _Pm of the m types of hydrogen is set to a condition that corresponds to the operating conditions of the actual plant. For example, _Pm is 5 to 18 MPa. The reaction period is, for example, 100 to 500 days.

(Method 1 for determining α and T _SOR )
In an actual plant or on a bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen/feed oil ratio, sulfur concentration in the feed oil, metal concentration in the feed oil, and sulfur concentration in the product oil are the assumed actual plant operating conditions. Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature. Examples of the assumed actual plant operating conditions include the operating conditions described in (How to determine Ec and T _B ) and (How to determine P _B and a). By plotting the reaction time on the horizontal axis and the measured reaction temperature on the vertical axis and drawing a regression line, a straight line expressed as y = a _α x + b _α is obtained. In this line, a _α is a value correlated with α in Equation 4, and b _α is T _SOR in Equation 4. Substituting b _α for T _SOR ′ and the measured reaction temperature for T _t ′ in Equation 7 gives the degree of deterioration Φ′ of the desulfurization reaction after any t days of reaction have elapsed. Plotting the logarithm of Φ' on the vertical axis against the reaction time on the horizontal axis yields a regression line expressed as y = -a _α 'x (where |-a _α '| = a _α '). _{a α} ' represents the degradation rate of the desulfurization reaction of the catalyst.

D is obtained by substituting the operating conditions S _P , S _F , LHSV, and P, and P _B , a, Ec, T _{B , and} T _SOR (i.e., b _α ) obtained by the above method into Equation 4. Φ _C is obtained by substituting the obtained D into Equation 3. In this case, Φ _C is a function of α. In Equation 2, if Φ _M =1, Φ = Φ _C , and Φ is a function of α. If the reaction time is plotted on the horizontal axis and the logarithm of Φ on the vertical axis, and a regression line is drawn while changing α so that α is 0 < α, multiple straight lines expressed as y = -a _α "x (|-a _α "| = a _α ") are obtained for each value of α. The α when a _α " on each straight line is equal to the above-mentioned a _α ' can be defined as the α in Equation 4.

(Method 2 for determining α and T _SOR )
A reaction similar to that in (Method 1 for Determining α and T _SOR ) is carried out to obtain a straight line expressed by y = a _α x + b _α , and b _α is defined as T _SOR in the above formula 4. D is determined by substituting the operating conditions S _P , S _F , LHSV, and P, and P _B , a, Ec, T _{B , and} T _SOR (i.e., b _α ) determined by the above method into the above formula 4. Φ _C is obtained by substituting the determined D into the above formula 3. In this case, Φ _C is a function of α. If Φ _M = 1 in the above formula 2, Φ = Φ _C , and Φ is a function of α. If the obtained Φ is substituted into Φ' in the above formula 7 and T _SOR (i.e., b _α ) is substituted into T _SOR ^' in the above formula 7 and rearranged for T _t ', T _t ' becomes a function of α. The α in the above formula 4 can be defined as the α when the ratio (T _t '/T _obs ) of T _t ' to the measured reaction temperature T _obs is 1. Similarly, it is preferable to calculate the ratios (T _t '/T _obs ) of T _t ' to N reaction temperatures T _obs , and define the α when the average of these is closest to 1 as the α in the above formula 4. N is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

(Modification of Coke Degradation Function 1)
The following describes a modified example of the coke deterioration function 1. As the coke deterioration function 1, a coke deterioration function 1-1 expressed by the following formula 10 may be used.

Φ _C =exp(-D't) Equation 10
In the above formula 10, D' is the deterioration coefficient of coke, which is an active species in the desulfurization reaction of the catalyst, and t is the number of days elapsed since the reaction began.

D' can be calculated using the following formula 11.

In the above formula 11, α' is the catalyst constant of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of coke on the catalyst), S _F is the sulfur concentration (mass%) in the feed oil after t days of reaction, S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feed oil containing atmospheric distillation residue, LHSV is the liquid hourly space velocity (h ^-1 ) after t days of reaction, P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, G _B is the reference hydrogen/feed oil ratio (Nm ³ /kL), and G is the hydrogen/feed oil ratio (Nm ³ /kL), b is the hydrogen/feed oil ratio coefficient, Ec is the activation energy of coke deterioration (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), T _B is the reference reaction temperature (K), and T _SOR is the required temperature on day 0 (K).

S _F , S _P , LHSV, and P in the above formula 11 are the same as those in the above formula 4. In the above formula 11, G is a value substituted based on the information on the feedstock oil and the information on the operating conditions acquired in the above-mentioned information acquisition step. Specifically, G can be calculated by dividing the hydrogen supply rate (Nm ³ /hour) by the feedstock oil supply rate (kL/hour).

In this specification, "reference hydrogen/feed oil ratio" refers to the standard hydrogen/feed oil ratio under actual reaction conditions. It is calculated as the average hydrogen/feed oil ratio used when determining the hydrogen/feed oil ratio coefficient b, which will be described later.

In the above formula 11, the term expressed by (G _B /G) ^b is a term that indicates dependency on the hydrogen/feed oil ratio, and as described above, becomes a constant when G is a set value and operation is performed under constant conditions.

P _B , a, Ec, T _B , and T _SOR can be calculated in the same manner as described above for Equation 4. How to calculate G _B , b, and α' will be described below.

_GB and b, like P _B , a, Ec, _TB and _TSOR, are parameters determined depending on the catalyst used, and may be determined while performing the reaction in an actual reaction system, or may be determined in advance on a bench scale based on the operating conditions of the actual reaction system. In this embodiment, it is preferable to determine them in advance on a bench scale based on the operating conditions of the actual reaction system. Hereinafter, how to determine _GB and b will be described.

(How to find _GB and b)
The method for determining the basic deterioration parameters in this embodiment is based on the deterioration behavior of the desulfurization reaction of the catalyst analyzed from data obtained from the reaction in the above-mentioned actual plant or from a bench-scale reaction based on the operating conditions of the actual plant.

The reaction is carried out for a certain period of time under constant conditions of LHSV, hydrogen partial pressure, sulfur concentration in the feed oil, metal concentration in the feed oil, and sulfur concentration in the product oil, and a hydrogen/feed oil ratio of G _h . Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature in order to maintain a constant sulfur concentration in the product oil. By plotting the reaction time on the horizontal axis and the measured reaction temperature on the vertical axis and drawing a regression line, a straight line expressed as y = a _h x + b _h (0 < a _h ) is obtained. b _h on this line is T _SOR ' in the above-mentioned equation 7. By substituting b _h for T _SOR ' and the measured reaction temperature for T _t ' in the above-mentioned equation 7, the deterioration degree Φ' of the desulfurization reaction after any t days of reaction has elapsed can be obtained. Plotting the logarithm of Φ' on the vertical axis against reaction time on the horizontal axis yields a regression line expressed as y = _-ah'x (| _-ah '| = _ah '), where _ah ' represents the degradation rate of the catalyst desulfurization reaction.

The same reaction is carried out for h types of hydrogen/feed oil ratios _Gh , h a _h and b _h are determined in the same manner, and h a _h ' are obtained by the same method as above. h is an integer of 3 or more. The larger the number of h, the more accurate b can be obtained. On the other hand, if the number of h is too large, it takes a long time to obtain b, which is not efficient. In this embodiment, h is preferably 3 to 20, and more preferably 3 to 10.
The h _a 's and G _h's thus obtained are respectively substituted into the following formula 12. The following formula 12 is an equation that can calculate the hydrogen/feed oil ratio coefficient and the reference hydrogen/feed oil ratio, and was first discovered by the inventors of the present application based on the operating results of an actual plant, etc.

ln( _ah ')=-bln( _Gh )+B3 Equation 12
In the formula 12, B3 can be 0.

For h combinations of a _h ' and G _h , ln(a _h ') is plotted on the vertical axis and ln(G _h ) on the horizontal axis, a regression line is drawn, and the slope is determined. This slope is the hydrogen/feed oil ratio coefficient b.

Moreover, _GB can be obtained by averaging the above h types of hydrogen/feedstock ratios _Gh .

In determining b and _GB , the LHSV, hydrogen partial pressure, sulfur concentration in the feed oil, metal concentration in the feed oil, and sulfur concentration in the product oil are preferably set to conditions that correspond to the operating conditions of an actual plant.
Such an LHSV is, for example, 0.1 to 1.0 h ⁻¹ , the hydrogen partial pressure is, for example, 5 to 18 MPa, the sulfur concentration in the feed oil is, for example, 1 to 5 mass %, the metal concentration in the feed oil is, for example, 10 to 200 mass ppm, and the sulfur concentration in the product oil is, for example, 0.5 mass % or less.
Similarly, it is preferable that the hydrogen/feedstock ratio G _h of the h types is set to a condition that corresponds to the actual operating conditions. Such G _h is, for example, 170 to 1400 [Nm ³ /kL]. The reaction period is, for example, 100 to 500 days.

In addition, α′ can be calculated in the same manner as the method for calculating α described in the coke deterioration function 1 ((method 1 for calculating α and T _SOR ) and (method 2 for calculating α and T _SOR )), except that Equation 11 is used instead of Equation 4.

<Coke deterioration function 2>
In this embodiment, the coke deactivation function relating to the deterioration of the desulfurization reaction of the catalyst due to coke deposition is preferably coke deactivation function 2, expressed by the following equation 13, which is composed of an easily deactivated active species deactivation function relating to the deterioration of easily deactivated active species in the desulfurization reaction of the catalyst and a hardly deactivated active species deactivation function relating to the deterioration of hardly deactivated active species in the desulfurization reaction of the catalyst.

Φ _C = k ₁ × exp (-D ₁ t) + k ₂ × exp (-D ₂ t) Equation 13
In Equation 13, _k1 is the active site coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst, _k2 is the active site coefficient of the hardly deactivated active species in the desulfurization reaction of the catalyst, and the active site coefficients represent the relative reaction rate constants of the desulfurization reaction of both active species. _D1 is the deterioration coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst due to coke, _D2 is the deterioration coefficient of the hardly deactivated active species in the desulfurization reaction of the catalyst due to coke, t is the number of days elapsed since the reaction began, and _k1 + _k2 = 1.

As mentioned above, in the hydrotreating reaction of atmospheric residual oil, catalyst degradation occurs due to coke buildup, so operation must be carried out at elevated reaction temperatures to maintain the sulfur content of the resulting oil below a certain level. In the hydrotreating reaction of atmospheric residual oil, the reaction temperature rises rapidly at the beginning of the reaction. This rapid rise in reaction temperature indicates rapid catalyst degradation at the beginning of the reaction. On the other hand, from the middle of the reaction onwards, the reaction temperature rises gradually. This gradual rise in reaction temperature indicates gradual catalyst degradation at the middle of the reaction onwards.

In other words, the profile of reaction temperature versus reaction time suggests that in the hydrotreating reaction of atmospheric distillation residue, the catalyst deteriorates rapidly at the beginning of the reaction, followed by gradual deterioration from the middle of the reaction onwards.

Based on the above-mentioned profile of reaction temperature versus reaction time, the inventors of the present application further improved coke deactivation function 1 and discovered coke deactivation function 2, based on the assumption that the catalyst contains active species that are easily deactivated by coke in the early stages of the reaction and active species that are difficult to deactivate in the middle or later stages of the reaction. As a result, they found that coke deactivation function 2 makes it possible to calculate the degree of catalyst deactivation by coke more accurately than coke deactivation function 1. Easily deactivated active species in the desulfurization reaction are active species that lose activity mainly in the early stages of the reaction, and difficult to deactivate active species in the desulfurization reaction are active species that lose activity in the middle or later stages of the reaction.

In the formula 13, _k1 represents the active site coefficient of the active species that is easily deactivated in the desulfurization reaction of the catalyst, _and k2 represents the active site coefficient of the active species that is difficult to deactivate in the desulfurization reaction of the catalyst. _k1 and _k2 are constants specific to the catalyst, and their determination will be described later.

_D1 can be calculated by the following formula 14, and _D2 can be calculated by the following formula 15.

In the above formulas 14 and 15, S _F is the sulfur concentration (mass%) in the feedstock oil after t days of reaction, S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, LHSV is the liquid hourly space velocity (h ⁻¹ ) after t days of reaction, P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol · K)), T _B is the reference reaction temperature (K), and T _SOR is the required temperature on day 0 (K).
In the above formula (14), _α1 is a catalytic constant of the easily deactivated active site of the desulfurization reaction (a constant representing the rate of deterioration of the desulfurization reaction due to coke on the catalyst), and in the above formula (15), _α2 is a catalytic constant of the hardly deactivated active site of the desulfurization reaction (a constant representing the rate of deterioration of the desulfurization reaction due to coke on the catalyst).

In the above-mentioned formulas 14 and 15, S _F , S _P , LHSV, and P are values substituted based on the information on the feed oil, the information on the product oil, and the information on the operating conditions acquired in the above-mentioned information acquisition step, as in the explanation of the above-mentioned formula 4. Note that the LHSV can be calculated by dividing the feed oil supply rate (volume/h) by the catalyst loading amount (volume).

As described above, S _F , LHSV, and P are controllable parameters. Furthermore, S _P is the sulfur concentration of the target product oil. That is, the deterioration coefficient due to coke of easily deactivated active species in the desulfurization reaction of the catalyst and the deterioration coefficient due to coke of less easily deactivated active species in the desulfurization reaction of the catalyst under the reaction conditions of S _F , S _P , LHSV, and P can be calculated using the above equations 14 and 15. The method for determining n, which is the reaction order of the hydrotreating reaction of feedstock oil containing atmospheric distillation residue, will be described later.

(How to determine basic coke deterioration parameters)
In the above-mentioned formulas 14 and 15, α ₁ , α ₂ , P _B , a, Ec, T _B , and T _SOR are constants, as in the above-mentioned formula 4, and these parameters are collectively referred to as the "basic coke deterioration parameter 2." The basic coke deterioration parameter 2 is a parameter determined depending on the catalyst used, and may be determined while performing a reaction in an actual reactor, or may be determined in advance on a bench scale based on the actual reactor operating conditions. In this embodiment, it is preferable to determine it in advance on a bench scale based on the actual reactor operating conditions. In the above-mentioned formulas 14 and 15, P _B , a, Ec, and T _B can be determined by the same method as in the above-mentioned formula 4.
On the other hand, α ₁ , α ₂ and T _SOR can be calculated, for example, by the following two methods. In addition, the active site coefficient k ₁ of the easily deactivated active species in the desulfurization reaction of the catalyst and the active site coefficient k ₂ of the hardly deactivated active species in the desulfurization reaction of the catalyst in the above formula 13 can also be calculated simultaneously as follows.

(Method 1 for determining α ₁ , α _{2 ,} T _SOR , k ₁ , and k ₂ )
In an actual plant or on a bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen/feed oil ratio, sulfur concentration in the feed oil, metal concentration in the feed oil, and sulfur concentration in the product oil are the expected operating conditions of the actual plant. Because the catalyst deteriorates during the reaction, operation is carried out while increasing the reaction temperature. Reaction time is plotted on the horizontal axis and reaction temperature on the vertical axis. When drawing a regression line between these plots, as described above, two lines are obtained: one line expressed as _{y =} a ₁ x + b _1, which correlates with the rapid increase in reaction temperature in the early stage of the reaction (x 1 to x n ), and the other line expressed as y = a ₂ x + b ₂ , which correlates with the gradual increase in reaction temperature from the middle stage of the reaction onwards (x _n+1 to x _m ). In the above formula, a ₁ > a ₂ > 0, b ₁ < b ₂ , and x ₁ < x _n < x _n+1 < x _m . x _n and x _m represent the reaction time relative to the n(m)th plot from the start of the reaction.

The above-mentioned _a1 is a value correlated with _α1 , _b1 is a value correlated with _k1 + _k2 , and is T _SOR . Furthermore, _a2 is a value correlated with _α2 , and _b2 is a value correlated with _k2 . Next, the intersection point (x _ip , y _ip ) at y = a ₁ x + b ₁ and y = a ₂ x + b ₂ is calculated. This intersection point represents the inflection point of y = a ₁ x + b ₁ and y = a ₂ x + b _2. In other words, up to (x _ip , y ip ), only active species that are easily deactivated in the desulfurization reaction of the catalyst are considered to exist, and from (x _ip , _{y ip} ), two active species are considered to exist: an active species that is easily deactivated in the desulfurization reaction of the catalyst and an active species that is difficult to deactivate in the desulfurization reaction of the catalyst.

In Equation 7, substituting _b1 for T _SOR ' and substituting the reaction temperature for T _t ' gives the degree of deterioration Φ' of the desulfurization reaction after any t days of reaction. Plotting the reaction time on the horizontal axis and the logarithm of Φ' on the vertical axis and drawing a regression line from x ₁ to x _ip gives a line expressed as y = -a ₁ 'x (|-a ₁ '| = a ₁ '). Furthermore, drawing a regression line from x _ip to x _m gives a line expressed as y = -a ₂ 'x -b ₂ ' (|-a ₂ '| = a ₂ ' and |-b ₂ '| = b ₂ '). _{a 1} ' is a value correlated with α ₁ , a ₂ ' is a value correlated with α ₂ , and b ₂ ' is a value correlated with k ₂ .

_k2 can be found by substituting _b2 ' obtained from the regression line described above into the following formula 16. Since _k1 is _k1 + _k2 = 1, k1 can be found from _k1 = 1 - _k2 .
k ₂ =exp(-b ₂ ') Equation 16

D1 and D2 are obtained by substituting the operating conditions S _P , _SF , LHSV, and P, and P _B , a, Ec, T _B , and T _SOR (b ₁ ) obtained by the above method into the above equations ₁₄ and _15. Φ _C is obtained by substituting the obtained D ₁ , D ₂ , k ₁ , and k ₂ into the above equation 13. In this case, Φ _C is a function of α ₁ and α _2. If Φ _M =1 in the above equation 2, then Φ = Φ _C , and Φ is a function of α ₁ and α ₂ . If the reaction time is plotted on the horizontal axis and the logarithm of Φ on the vertical axis, and a regression line is drawn from x ₁ to x _ip while setting α ₂ =0 and changing α ₁ so that 0 < α ₁ , multiple lines expressed as y = -a _α1 ''x (|-a _α1 ''| = a _α1 '') will be obtained for each value of α _1. The α 1 when a _α1 '' on each line is equal to the above-mentioned a _{1 '} can be taken as the α ₁ in the above formula 14.
Next, by substituting the obtained α1 into Φ _C (Φ), which is a function of _α1 and _α2 obtained by the _above method, and drawing a regression line from x _ip to x _m while changing _α2 so that 0 < _α2 , multiple lines expressed as y = -a _α2 "x - b _α2 " (|-a _α2 "| = a _α2 ") are obtained for each value of _α2 . The _α2 when a α2 " on each line is equal to the above-mentioned a ₂ ' can be taken as _{the α2} in the above formula 15.

(Method 2 for determining α ₁ , (α ₂ ) _, T _SOR , k ₁ , and k ₂ )
In this embodiment, _α2 is calculated simultaneously with the basic deterioration parameters of the metal in the metal deterioration function described later, so _α1 , T _SOR , _k1 , and _k2 are calculated. The method for calculating _α2 in this embodiment will be described later. T _SOR , _k1 , and _k2 are calculated in exactly the same way as (method 1 for calculating _α1 , α2 _, T _SOR , _k1 , and _k2 ). In (Method 1 for determining _α1 , α2 _, T _SOR , _k1 , and _k2 ), for _ΦC , which is a function of the obtained _α1 and _α2 , if the reaction time is plotted on the horizontal axis and the logarithm of _ΦC on the vertical axis, and a regression line is drawn _{from x1} to _xip by setting _α2 = 0 and changing α1 so that 0 < _α1 , multiple lines expressed as y = -a _α1-1 "x (|-a _α1-1 "| = a _α1-1 ") are obtained for each value of _α1 . The _α1 when a _α1-1 " on each line is equal to the above-mentioned _a1 ' can be taken as the _α1 in formula 14.

(Method 3 for determining α ₁ , α _{2 ,} T _SOR , k ₁ , and k ₂ )
The same reaction as in (Method 1 for determining α ₁ , α _{2 ,} T _SOR , k ₁ , and k ₂ ) is carried out to obtain T _SOR (b ₁ ). D 1 and D 2 are obtained by substituting the operating conditions S _P , _SF , LHSV, and P, and P _B , a, Ec, T _B , and T _SOR (b ₁ ) determined by the above method into Equations 14 and 15. Φ _{C is obtained by substituting the determined D 1 and D 2 into} Equation 13. In this case, Φ _C is _a function of α ₁ , α ₂ , k ₁ , and k _2. In Equation 2, if Φ _M =1, then Φ = Φ _C , and Φ is a function of α ₁ , α ₂ , k ₁ , and k ₂ . Substituting the obtained Φ for Φ' in the above formula 7 and T _SOR (i.e., b ₁ ) for T _SOR ' in the above formula 7 and rearranging for T _t ', T _t ' becomes a function of α ₁ , α ₂ , k ₁ , and k _2. If α ₂ is set to 0 and k ₂ = 1 - k ₁ , T _t ' becomes a function of α ₁ and k _1. The combination of α 1 and k ₁ when the ratio of T _t ' to the actually measured reaction temperature T _obs at x ₁ to x _ip (T _t '/T _obs ) is ₁ can be found, and this α ₁ can be used as α ₁ in the above formula 14. Note that k ₁ at this time is a provisional value. Similarly, it is preferable to calculate the ratio of T _t ' to M reaction temperatures T _obs (T _t '/T _obs ), and define α ₁ when the average of these is closest to 1 as α ₁ in the above formula 14. M is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.
Using the obtained _α1 , and setting _k1 = 1 - _k2 , _Tt ' becomes a function of _α2 and _k2 . The combination of α2 and _k2 when the ratio ( _Tt '/ _Tobs ) of Tt' to the measured reaction temperature _Tobs at _xip to _xm is 1 is determined, and _{these α2} and _k2 can be used as _{α2 and k2} in the above formula 15. By substituting the obtained _k2 into _k1 = 1 - _k2 , _k1 is determined, and this _k1 can be used as _k1 in the above formula 14. Similarly, it is preferable to calculate the ratios ( _Tt '/ _Tobs ) of _Tt ' to L reaction temperatures _Tobs , and use the _α2 and _k2 when their average is closest to 1 as the _α2 and _k2 in the above formula 15. Furthermore, it is preferable to use the _k1 determined from the obtained _k2 as the _k1 in the above formula 14. L is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

In this way, in order to find α ₁ , α _{2 ,} T _SOR , k ₁ , and k ₂ , it is necessary to obtain y = a ₁ x + b ₁ and y = a ₂ x + b _2. For example, y = a ₁ x + b ₁ and y = a ₂ x + b ₂ can be found as follows.

Using the method described above, the reaction time is plotted on the horizontal axis and the reaction temperature on the vertical axis. By drawing a regression line from the start of the reaction to the end of the reaction, a straight line expressed as y = a'x + b' is obtained. This line does not take into account the inflection point. Plots are sequentially deleted from the end of the reaction, and the y = a'x + b' is adjusted so that the correlation coefficient approaches 1, resulting in y = _a1'x + _b1 '. Similarly, plots are sequentially deleted from the start of the reaction, and the y = a'x + b' is adjusted so that the correlation coefficient approaches ₁ , resulting in y = _a2'x + _b2 '. The lines where the average correlation coefficients _{of y = a1'x +} b1' and y = a2'x + _b2 ' are closest to 1 are y = _a1x + _b1 and _y = a2x + _b2 . All plots belong to either y=a ₁ x+b ₁ or y=a ₂ x+b ₂ .

The reaction time required to obtain y = a ₁ x + b ₁ and y = a ₂ x + b ₂ is usually 100 days or more. In general, it is sufficient to carry out the reaction until the correlation coefficient of y = a'x + b' becomes 0.5 or more.

(Modification of Coke Degradation Function 2)
The following describes a modified example of the coke deterioration function 2. As the coke deterioration function 2, a coke deterioration function 2-1 expressed by the following equation 17 may be used.

Φ _C = k ₁ × exp (-D ₁ 't) + k ₂ × exp (-D ₂ 't) Equation 17
In the above formula 17, k ₁ , k ₂ , and t are the same as in the above formula 13, D ₁ ' is the deterioration coefficient of coke, an active species that is easily deactivated in the desulfurization reaction of the catalyst, and D ₂ ' is the deterioration coefficient of coke, an active species that is difficult to deactivate in the desulfurization reaction of the catalyst.

D ₁ ' can be calculated from the following formula 18, and D ₂ ' can be calculated from the following formula 19.

In the formulas 18 and 19, S _F , S _P , n, LHSV, P _B , P, a, Ec, R, T _B , and T _SOR are the same as in the formulas 14 and 15, and G _B , G, and b are the same as in the formula 11. In the formula 18, α ₁ ' is a catalytic constant of the easily deactivated active site of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst), and in the formula 19, α ₂ ' is a catalytic constant of the hardly deactivated active site of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst).

P _B , a, Ec, T _B , and T _SOR can be calculated in the same manner as described in Equation 14 and Equation 15, and G _B and b can be calculated in the same manner as described in Equation 11.

In addition, α ₁ ' and α ₂ ' can be calculated in the same manner as for calculating α 1 and α ₂ described in the coke deterioration function 2 of the desulfurization reaction, except that Equation 17 is used instead of Equation 13, Equation 18 is used instead of Equation 14, and Equation ₁₉ is used instead of Equation 15.

<Metal Deterioration Function>
The metal deterioration function is not particularly limited as long as it is a function that can calculate the degree of deterioration of the desulfurization reaction related to metal deterioration of the catalyst, and an example thereof is metal deterioration function 1 expressed by the following formula 20. Metal deterioration function 1 expressed by formula 20 is a metal deterioration function described in a non-patent document (Collection of Chemical Engineering Papers, Vol. 24, No. 4 (1998), p. 656).

Equation 20 is a deterioration function that expresses the degree of deterioration of the desulfurization reaction due to a decrease in the diffusion rate in the catalyst pores as the rate of decrease in the catalyst effectiveness coefficient. Φ _M is the degree of deterioration, η is the catalyst effectiveness coefficient, and t _end is the number of days (days) until the reaction ends and the catalyst pores become clogged. η is greater than 0 and equal to or less than 1, and when η = 1, Φ _M = 1. η takes two values: 1 and a constant greater than 0 but less than 1. η is 1 at the beginning of the reaction and becomes a constant greater than 0 but less than 1 from the middle of the reaction onwards.

As mentioned above, in the hydrotreating reaction of feedstocks containing atmospheric residue, catalyst degradation occurs due to metal deposition. Therefore, in order to maintain the sulfur content of the resulting oil below a certain level, operation must be performed at elevated reaction temperatures. This phenomenon of catalyst degradation due to metal deposition can be explained by a decrease in the rate of diffusion of the feedstock into the catalyst pores. In other words, in the hydrotreating reaction of atmospheric residue, the feedstock must diffuse into the catalyst pores and access the active sites. If the diffusion rate is sufficiently higher than the reaction rate, the feedstock can access all the active sites. However, if the diffusion rate is slower than the reaction rate, the feedstock cannot access all the active sites, and all the active sites do not function effectively. The diffusion rate decreases over time as the catalyst pores become clogged with metal deposition.

The degree to which the active sites within the catalyst pores are effectively utilized is determined by the relationship between the reaction rate and the diffusion rate. This relationship can be theoretically expressed by the catalyst effectiveness coefficient η. If there is no diffusion inhibition and essentially all of the active sites within the catalyst pores are utilized, η is 1. On the other hand, if essentially none of the active sites within the catalyst pores are utilized, η is less than 1. And if only the active sites near the outer surface of the catalyst are utilized, η approaches 0.

As mentioned above, the profile of reaction temperature versus reaction time suggests that in the hydrotreating reaction of atmospheric distillation residue, the catalyst deteriorates rapidly at the beginning of the reaction, followed by gradual deterioration from the middle of the reaction onwards.

As described above, the inventors of the present application discovered the coke deactivation function based on the assumption that there are easily deactivated active species for desulfurization reactions that are deactivated by coke in the early stages of the reaction, and less easily deactivated active species for desulfurization reactions that are deactivated by coke from the middle stage onwards. Here, it is believed that a decrease in activity due to metal deposition also occurs from the middle stage onwards, and the gradual deterioration of the catalyst from the middle stage onwards is thought to be due to the deactivation of less easily deactivated active species for desulfurization reactions that are deactivated by coke, and metal deposition. Based on the above-mentioned reaction temperature versus reaction time profile, the inventors of the present application discovered the metal deactivation function based on the assumption that the gradual deterioration of the catalyst from the middle stage onwards is due to the deactivation of less easily deactivated active species for desulfurization reactions that are deactivated by coke, and metal deposition. As a result, they discovered that by combining the coke deactivation function and the metal deactivation function, it is possible to more accurately calculate the degree of catalyst deactivation for desulfurization reactions.

In the above formula 20, η and t _end are constants (however, η becomes two types of constants depending on the reaction time). Hereinafter, these parameters will be collectively referred to as "basic deterioration parameters of metals." The basic deterioration parameters of metals are parameters determined depending on the catalyst used, and may be determined while performing a reaction in an actual machine, or may be determined in advance on a bench scale based on the operating conditions of the actual machine. In this embodiment, it is preferable to determine the parameters in advance on a bench scale based on the operating conditions of the actual machine.
Below, examples of how to obtain the basic deterioration parameters η and t _end will be explained, but the present invention is not limited to these.

(Method 1 for finding η, t _end , α ₂ )
In this embodiment, η, t _end , and _α2 are determined by combining this with (Method 2 for determining α ₁ , (α ₂ ) _, T _SOR , k ₁ , and k ₂ ). Using a method similar to that described above in (Method 2 for determining α ₁ , (α ₂ ) _, T _SOR , k ₁ , and k ₂ ), two lines, one represented by y = a ₁ x + b ₁ corresponding to the rapid increase in reaction temperature in the early stage of the reaction (x ₁ to x _n ), and the other represented by y = a ₂ x ₊ b ₂ corresponding to the gradual increase in reaction temperature from the middle stage of the reaction onwards (x _n+1 to x m ), as well as the inflection points (x _ip , y _ip ). From (x _ip , y _ip ), two coke deactivation active species, namely, an active species that is easily deactivated in the desulfurization reaction and an active species that is difficult to deactivate in the desulfurization reaction, are present, and it is considered that metal deterioration is occurring. That is, up to the inflection point (x _ip , y _ip ), η is 1, and from the above formula 20, Φ _M is 1. Therefore, up to the inflection point (x _ip , y _ip ), the above formula 2 is expressed as Φ = Φ _C. On the other hand, after the inflection point (x _ip , y _ip ), η becomes a constant smaller than 1.

Using the same method as described above in (Method 2 for finding α ₁ , (α ₂ ) _, T _SOR , k ₁ , and k ₂ ), a regression line is drawn from x _ip to x _m to obtain a line expressed as y = -a ₂ 'x-b ₂ ' (where |-a ₂ '| = a ₂ ' and |-b ₂ '| = b ₂ ').

D1 and D2 are obtained by substituting the operating conditions S _P , _SF , LHSV, and P, and P _B , a, Ec, T _B , T _SOR (b ₁ ), and α ₁ obtained by the above method into the above equations 14 and _15. Φ _C is obtained by substituting the obtained D _{1 and} D ₂ and k ₁ and k ₂ obtained by the above method into the above equation 13. In this case, Φ _C is a function of α _2. Φ is obtained by substituting this Φ _C and Φ _M from the above equation 20 into the above equation 2. In this case, Φ is a function of α ₂ , η, and t _end . When the reaction time is plotted on the horizontal axis and the logarithm of Φ on the vertical axis, and the combinations of (α ₂ , η, t _end ) are changed with α ₂ in the range of 0 < α ₂ , η in the range of 0 < η < 1, and x _ip < t _end , and a regression line from x _ip to x _m is drawn, multiple lines expressed as y = -a _α3 "x - b _α3 " (|-a _α3 "| = a _α3 ") are obtained for each combination of (α ₂ , η, t _end ). The _{α 2} when a _{α3 " in each line and the above-mentioned a 2} ' are equal can be taken as the α ₂ in formula 15. Furthermore, the combination of (η, t _end ) when b _α3 " in each line and the above-mentioned b ₂ ' are equal can be taken as the η, t _end in formula 20.

(Method 2 for determining η and t _end )
This embodiment can be applied when _α2 is determined in advance using the above-mentioned method, with Φ _M =1. Using a method similar to that described above in (Method ₁ for Determining α1, α2 _, T _SOR , _k1 , and _k2 ), two lines, one represented by y = _a1x + b1 corresponding to the rapid increase in reaction temperature in the early stage of the reaction (x1 to _xn ), and the other represented by y = _a2x + _b2 corresponding to the gradual increase in reaction temperature from the middle stage of the reaction onwards ( _{xn +1} to _{xm )} , as well as an inflection point ( _xip , _yip ), are obtained. From ( _xip , _yip ), it is apparent that two coke deactivation active species exist: one readily deactivated active species for the desulfurization reaction and one resistant to deactivation active species for the desulfurization reaction, and it is therefore assumed that metal degradation is occurring. That is, up to the inflection point (x _ip , y _ip ), η is 1, and from the above equation 20, Φ _M is 1. Therefore, up to the inflection point (x _ip , y _ip ), the above equation 2 is expressed as Φ = Φ _C. On the other hand, after the inflection point (x _ip , y _ip ), η becomes a constant smaller than 1.

Using the same method as described above in (Method 1 for finding α ₁ , α _{2 ,} T _SOR , k ₁ , and k ₂ ), a regression line is drawn from x _ip to x _m to obtain a line expressed as y = -a ₂ 'x-b ₂ ' (where |-a ₂ '| = a ₂ ' and |-b ₂ '| = b ₂ ').

D1 and D2 are obtained by substituting the operating conditions S _P , S _F , LHSV, and P, and P _B , a, Ec, T _B , T _SOR (b ₁ ), α ₁ , and α ₂ obtained by the above method into the above equations 14 and _15. Φ _C is obtained by substituting the obtained D _{1 and} D ₂ and k ₁ and k ₂ obtained by the above method into the above equation 13. Φ is obtained by substituting this Φ _C and Φ _M of the above equation 20 into the above equation 2. In this case, Φ is a function of η and t _end . By plotting the reaction time on the horizontal axis and the logarithm of Φ on the vertical axis, changing the combination of (η, t _end ) within the range of 0<η<1 and x _ip <t _end , and drawing a regression line from x _ip to x _m , multiple lines expressed as y = -a _α3-1 "x-b _α3-1 " (|-a _α3-1 "| = a _α3-1 ") can be obtained for each combination of (η, t _end ). The combination of (η, t _end ) when b _α3-1 ″ on each line and the above-mentioned b ₂ ′ are equal can be used as η and t _end in the above formula 20. Note that although the above description has been given using coke deterioration function 2, η and t _end can be obtained in the same manner for coke deterioration function 1, coke deterioration function 1-1, and coke deterioration function 2-1. In this case, Φ _C obtained from coke deterioration function 1, coke deterioration function 1-1, and coke deterioration function 2-1 can be used.

Another example of a metal deterioration function is metal deterioration function 2, expressed by the following equation 21:

In the above formula (21), η is the catalyst effectiveness coefficient, MOC is the metal deposition amount (unit: wt%) after any reaction for t days, and _MC is the maximum metal deposition amount (unit: wt%) of the catalyst. That is, _MC represents the metal deposition amount of the catalyst at the time t _end of the above formula (20).

Metal Deterioration Function 2 is an equation derived based on Metal Deterioration Function 1. The derivation of Metal Deterioration Function 2 is explained below.

The MOC in equation 21 above is expressed by equation 22 below.

In Equation 22, WHSV is the average weight hourly space velocity (h ^-1 ) from the start of the reaction until any t days have passed since the reaction began, M _F is the average metal concentration (weight ppm) in the feedstock oil from the start of the reaction until any t days have passed since the reaction began, M _P is the average metal concentration (weight ppm) in the product oil from the start of the reaction until any t days have passed since the reaction began, and t is the number of days elapsed since the reaction began. That is, [0.0024 x WHSV x (M _F - _{M p} )] represents the average amount of metal deposition (units) per day from the start of the reaction until any t days have passed since the reaction began.

From the above-mentioned equation 22, M _C in the above-mentioned equation 21 is expressed by the following equation 23.

In the above formula, WHSV, M _F and M _P are the same as in the above formula 22, and t _end is the number of days (days) that have passed since the reaction until the catalyst pores are blocked.

From the above formulas 22 and 23, t _end is expressed by the following formula 24.
t _end = Mc/(MOC/t) Equation 24

By substituting the above-mentioned formula 24 into the above-mentioned formula 20, the above-mentioned formula 21 can be derived.
According to the metal deterioration function 2, t _end can be determined from MOC and _MC .

(How to calculate MOC)
The MOC can be calculated by the above-mentioned formula 22. In the formula, WHSV, _MF , and _MP are values substituted based on the information on the feed oil, the information on the product oil, and the information on the operating conditions acquired in the above-mentioned information acquisition step. Note that the WHSV can be calculated by dividing the feed oil supply rate (weight/h) by the catalyst loading amount (weight).

As mentioned above, WHSV and M _F are controllable parameters. Furthermore, M _P is the metal concentration of the target product oil. That is, the metal degradation function under the reaction conditions of the above WHSV, M _F and M _P can be calculated using the above equation (21).

(How to find _MC )
M _C is a value specific to the catalyst and can be determined by methods known in the art. As an example of how to determine M _C , for example, in an actual or bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen/feed oil ratio, sulfur concentration in the feed oil, metal concentration in the feed oil, and sulfur concentration in the product oil are the expected actual operating conditions. Because the catalyst deteriorates during the reaction, operation is carried out while increasing the reaction temperature. Examples of actual operating conditions include the operating conditions described in (How to determine Ec and T _B ) and (How to determine P _B and a). If the reaction is continued for a long period of time, the sulfur concentration in the product oil will not reach the specified value, even if the reaction temperature is set to the maximum temperature used for the equipment (e.g., 410°C). The reaction is continued in this state, and when the sulfur concentration in the feed oil = the sulfur concentration in the product oil, the reaction is stopped and the catalyst is withdrawn. The metal concentration of the withdrawn catalyst is measured, and the obtained value can be used as M _C . From the viewpoint of obtaining _MC in a short period of time, it is possible to use feedstock oil with an extremely high metal concentration and operate at an LHSV higher than the actual operating conditions.

In metal deterioration function 2, t _end can be determined using MOC and _MC . Therefore, fitting in the above-mentioned method of determining η, t _end , _α2 becomes easier. Specifically, in the above-mentioned method of determining η, t _end , _α2 , it was necessary to determine the combination of (η, t _end ) when b _α3 " and b ₂ ' become equal values, but in metal deterioration function 2, t _end is determined in advance using MOC and _MC , so it is only necessary to determine η when b _α3 " and b ₂ ' become equal values, making it possible to determine η more simply and with higher accuracy.

(η switching timing)
As described above, η can take two values: 1, or a constant greater than 0 but less than 1 obtained by the above-described method. η is 1 at the beginning of the reaction, and is a constant greater than 0 but less than 1 from the middle stage of the reaction onwards. Two examples of the timing for switching η from 1 to the constant greater than 0 but less than 1 will be described below, but the present invention is not limited to these two examples. The information processing method of this embodiment preferably includes a step of determining the timing for switching η. In this case, the information on the operating conditions acquired in the above-described information acquisition step preferably includes information on the actual measured value of the reaction temperature. The step of determining the timing for switching η is executed, for example, by the cracked light oil yield calculation device 1 of this embodiment. For example, this step is executed by the calculation unit 13 in the computer main body 12.

(η switching timing 1)
The reaction is started with Φ _M =1. In this case, Φ = Φ _C. Using this Φ, the reaction temperature _Tt required to satisfy the predetermined conditions is calculated in the reaction temperature calculation step described below, and the reaction is continued at this reaction temperature _Tt . From the middle stage of the reaction onwards, even if the reaction temperature is set to _Tt , the predetermined conditions (sulfur concentration in the predetermined product oil) will no longer be satisfied. In this case, the reaction temperature is increased to search for a reaction temperature that satisfies the predetermined conditions (sulfur concentration in the predetermined product oil). The reaction temperature at this time is assumed to be Tt + Z (°C). When Z becomes 2 (°C) or more, it is preferable to switch η from 1 to the constant greater than 0 and less than 1.

(η switching timing 2)
The reaction is started with Φ _M =1. In this case, Φ = Φ _C. Using this Φ, the reaction temperature T _t required to satisfy the predetermined conditions is calculated in the reaction temperature calculation step described below, and the reaction is continued at this reaction temperature T _t . As described above, from the middle stage of the reaction onwards, even if the reaction temperature is set to T _t , the predetermined conditions (sulfur concentration in the predetermined product oil) will no longer be satisfied. In this case, the reaction temperature is increased to search for a reaction temperature that satisfies the predetermined conditions (sulfur concentration in the predetermined product oil). Φ(Φ _t ) is obtained by substituting the T _SOR determined by the above method for T _SOR in Equation 25 described below, and the T _t determined in the reaction temperature calculation step for T _t . Furthermore, Φ(Φ obs ) is obtained by substituting the T _SOR determined by the above method for T _SOR in Equation 25 described below, and the reaction temperature ( _measured value) that satisfies the above predetermined conditions (sulfur concentration in the predetermined product oil) for T _t . It is preferable to observe Φ _obs /Φ _t over time, and switch η from 1 to the constant greater than 0 and less than 1 when Φ _obs /Φ _t becomes 0.9 or less.

<Reaction temperature calculation step>
The reaction temperature calculation step of this embodiment is a step of calculating a reaction temperature necessary to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst. The reaction temperature is preferably calculated using a desulfurization rate equation based on the Arrhenius equation.

<Degradation rate equation for desulfurization reaction>
The deterioration rate equation for the desulfurization reaction is based on the Arrhenius equation expressed by the above-mentioned Equation 6. Similar to the calculation method for the above-mentioned Equation 7, the following Equation 25 is derived from the above-mentioned Equations 1 and 6.

In Equation 25, Φ is the degree of deterioration of the desulfurization reaction, Ea is the activation energy of desulfurization (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), _Tt is the required temperature (K) after t days of reaction, and T _SOR is the required temperature (K) on day 0.
By rearranging the above equation 25, the following equation 26 is obtained.

T _t (K) after t days of reaction can be obtained by substituting T _SOR and Φ obtained by the above-mentioned method into the above-mentioned formula 26. The activation energy of the desulfurization reaction in the above-mentioned formula 26 can be calculated as follows.

(How to calculate the activation energy of the desulfurization reaction)
The activation energy of the desulfurization reaction can be determined by a method known in the art based on the Arrhenius equation represented by the above-mentioned formula 6. An example will be described below.

First, the reaction order of the desulfurization reaction of feedstock oil containing atmospheric distillation residue oil is determined. The reaction temperature, hydrogen partial pressure, hydrogen/feedstock ratio, and sulfur concentration in the feedstock oil are constant, and the reaction is carried out under LHSV(x) conditions, and the sulfur concentration in the product oil is measured. In the desulfurization reaction rate equation expressed by the following equation 27, the sulfur concentration in the feedstock oil is substituted for _SF , the sulfur concentration in the resulting product oil for _SP , and LHSV(x) for LHSV. The result of the left-hand side obtained is plotted on the vertical axis, and 1/LHSV on the horizontal axis. In this case, the vertical axis is a function of n.

A similar reaction is carried out for x types of LHSV(x), and x of the above plots are obtained. Based on the obtained plots, a regression line is drawn passing through the origin to obtain a line expressed as y = cx. y is ((1/(n-1))((1/S _P ^n-1 )-(1/S _F ^n-1 ))), x is 1/LHSV, and c is k. The correlation function is calculated using Excel or similar software, and n is determined for which the correlation coefficient is closest to 1. The obtained n is the reaction order. Note that n can be calculated to one decimal place.

The above x is an integer of 3 or greater. The larger the number of x, the more accurate n can be obtained. On the other hand, if the number of x is too large, it takes a long time to obtain n, which is inefficient. In this embodiment, x is preferably 3 to 20, and more preferably 3 to 10.

In determining n, the reaction temperature, hydrogen partial pressure, hydrogen/feedstock ratio, and sulfur concentration in the feedstock are preferably set to conditions that correspond to the operating conditions of an actual plant.
Such a reaction temperature is, for example, 330 to 410°C, the hydrogen partial pressure is 5 to 15 MPa, the hydrogen/feedstock ratio is 170 to 1400 [Nm ³ /kL], and the sulfur concentration in the feedstock is 1 to 5 mass%.
Similarly, it is preferable that the x types of LHSV(x) are set to conditions that correspond to the actual operating conditions of the plant. Such LHSV(x) is 0.1 to 1.0 h ⁻¹ .

If the activation energy E in the Arrhenius equation expressed by Equation 6 above is taken as the desulfurization activation energy Ea and the natural logarithm of both sides is taken, the following equation (28) is obtained.

The reaction is carried out under constant conditions of hydrogen partial pressure, hydrogen/feed oil ratio, LHSV, and sulfur concentration in the feed oil at a reaction temperature T(y), and the sulfur concentration in the product oil is measured. The sulfur concentration in the feed oil is substituted for _SF , the sulfur concentration in the resulting product oil for _SP , LHSV for LHSV, and the obtained n in the desulfurization reaction rate equation expressed by Equation 27 are substituted for LHSV, and the reaction rate constant k is calculated. The obtained reaction rate constant is substituted into Equation 28, and the result (lnk) on the left side of the equation is plotted on the vertical axis and 1/T (1/T(y)) on the horizontal axis.

The same reaction is carried out for y different reaction temperatures T(y), and y of the above plots are obtained. A regression line is drawn from the resulting plots, and its slope is determined. Since this slope is Ea/R, the activation energy of desulfurization, Ea, can be determined by subtracting R from the slope.

The above y is an integer of 3 or greater. The larger the value of y, the more accurate Ea can be obtained. On the other hand, if the value of y is too large, it takes a long time to obtain Ea, which is inefficient. In this embodiment, y is preferably 3 to 20, and more preferably 3 to 10.

The hydrogen partial pressure, hydrogen/feed oil ratio, LHSV, and sulfur concentration in the feed oil used to determine Ea are preferably set to conditions that correspond to the operating conditions of an actual plant.
Such hydrogen partial pressure is, for example, 5 to 18 MPa, the hydrogen/feedstock ratio is 170 to 1400 [Nm ³ /kL], the LHSV is 0.1 to 1.0 h ⁻¹ , and the sulfur concentration in the feedstock is 1 to 4 mass %.
Similarly, it is preferable that the reaction temperature T(y) of the y types is set to a condition that conforms to the operating conditions of the actual equipment. Such T(y) is 330 to 410°C.

By substituting each parameter thus obtained into the above-mentioned formula 26, the reaction temperature _Tt required to achieve the predetermined reaction conditions can be obtained.

The ratio of the reaction temperature _Tt determined by the information processing method of this embodiment to the actually measured reaction temperature _Tobs , _Tt / _Tobs , is preferably 0.97 to 1.03, and more preferably 0.985 to 1.015, in ° C. When _Tt / _Tobs is within the above range, it can be determined that the reaction temperature has been estimated with high accuracy.

<Steps for calculating the amount of cracked light oil>
In the step of calculating the yield of cracked light oil in this embodiment, the yield of cracked light oil is calculated based on the reaction temperature _Tt and the degree of deterioration of the cracking reaction of the catalyst. The yield of cracked light oil is preferably calculated using a cracked light oil yield calculation function based on a first-order cracking reaction rate equation.

<Light cracked oil yield calculation function>
The function for calculating the yield of cracked light oil is expressed by the following equation 29.

In the above equation 29, C _t is the yield (mass%) of cracked light oil after t days of reaction, k _C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the reaction temperature T _t calculated in the above-mentioned reaction temperature calculation step for the catalyst (fresh catalyst) after 0 days of reaction ( ^i.e. , at the start of the reaction), Φ _D is the degree of deterioration of the cracking reaction, and LHSV is the liquid hourly space velocity (h ⁻¹ ) after t days of reaction.

In the above-mentioned formula 29, LHSV is a value substituted based on the information on the operating conditions acquired in the information acquisition step described above. Note that LHSV can be calculated by dividing the feedstock oil supply rate (volume/h) by the catalyst loading rate (volume). How to calculate _ΦD and kC0 _(Tt) will be described later.

The degradation degree of the decomposition reaction in the above formula 29 is expressed by the following formula 30.
Φ _D =k _Ct(T0) /k _C0(T0) Formula 30
In the above equation 30, k _C0(T0) is the reaction rate constant of the decomposition reaction of the catalyst (fresh catalyst) after 0 days of reaction (i.e., at the start of the reaction), and k _Ct(T0) is the reaction rate constant of the decomposition reaction of the catalyst after t days of reaction. Note that k _Ct(T0) and k _C0(T0) are the reaction rate constants of the decomposition reaction at the above-mentioned temperature T _SOR .

Equation 29 is derived based on the assumption that the cracking reaction of atmospheric distillation residue is a first-order reaction, and that only light cracked oil is produced by the cracking reaction. The method for deriving equation 29 is explained below.

The decomposition reaction rate equation is expressed by the following equation 31.
k _Ct(Tt) = ln(C _F /C _P )×LHSV Equation 31
In the above equation 31, k _{Ct (Tt)} is the reaction rate constant (h ⁻¹ ) of the catalytic cracking reaction at the reaction temperature T _t calculated in the above-mentioned reaction temperature calculation step after t days of reaction have elapsed, C _F is the atmospheric distillation residue concentration (mass%) in the feed oil after t days of reaction have elapsed, C _P is the atmospheric distillation residue concentration (mass%) in the product oil after t days of reaction have elapsed, and LHSV is the liquid hourly space velocity (h ⁻¹ ) after t days of reaction have elapsed.

Since C _F /C _P is dimensionless, if C _F is set to 1, the conversion rate C _t (%) of the cracking reaction after any t days of reaction is C _t = (1 - C _P ) × 100. Therefore, C _P can be expressed as C _P = 1 - C _t /100. As mentioned above, based on the premise that only cracked light oil is produced by the cracking reaction, the conversion rate C _t (%) also becomes the amount (mass%) of cracked light oil obtained. Substituting these values into the above formula 31, the following formula 32 is obtained.

When the above-mentioned formula 32 is summarized for _Ct , the following formula 33 is obtained.

From the above formula 30, the degradation degree of the decomposition reaction can also be expressed by the following formula 34.

Φ _D =k _Ct(Tt) /k _C0(Tt) Equation 34
In the above formula 34, k _C0(Tt) is the reaction rate constant of the decomposition reaction of the catalyst (fresh catalyst) after 0 days of reaction (i.e., at the start of the reaction), and k _Ct(Tt) is the reaction rate constant of the decomposition reaction of the catalyst after t days of reaction. Note that k _Ct(Tt) and k _C0(Tt) are the reaction rate constants of the decomposition reaction at the reaction temperature _Tt after t days of reaction calculated in the reaction temperature calculation step described above.

From the above-mentioned equation 34, k _Ct(Tt) =Φ _C ×k _C0(Tt) , and by substituting this value into the above-mentioned equation 33, the above-mentioned equation 29 is derived.

Next, how to obtain Φ _D and k _C0(Tt) will be described.

(How to calculate kC0 _(Tt) )
kC0 _(Tt) is a parameter (constant) determined depending on the catalyst used, and may be determined while performing the reaction in an actual reaction system, or may be determined in advance on a bench scale based on the operating conditions of the actual reaction system. In this embodiment, it is preferable to determine it in advance on a bench scale based on the operating conditions of the actual reaction system.
kC0 _(Tt) can be calculated by the following formula 35. The following formula 35 is based on the Arrhenius equation expressed by the above formula 6.

In the above formula 35, k _C0(T0) is the reaction rate constant (h ⁻¹ ) of the decomposition reaction of the catalyst (fresh catalyst) at the reaction temperature T _SOR after 0 days of reaction (i.e., at the start of the reaction), k _C0(Tt) is the reaction rate constant (h ⁻¹ ) of the decomposition reaction at the reaction temperature T _t after any t days of reaction calculated in the above-mentioned reaction temperature calculation step, E _D is the activation energy of the decomposition (kJ/mol), and R is the gas constant: 0.00831 (kJ/(mol·K)).

Since k _C0(T0) is the reaction rate constant of the decomposition reaction of the fresh catalyst at the reaction temperature T _SOR , it can be calculated using the following equation 36 based on the above equation 32.

In the above formula 36, C _t0 is the yield (mass %) of cracked light oil when the desulfurization reaction of atmospheric distillation residue is carried out using a fresh catalyst at a reaction temperature T _SOR , and LHSV is the liquid hourly space velocity (h ⁻¹ ).

That is, k _C0(T0) can be calculated from the above-mentioned Equation 36 by carrying out a hydrotreating reaction on a bench scale using a fresh catalyst, setting the reaction temperature to the above-mentioned T _SOR , and performing the hydrotreating reaction at LSHV, which is the operating condition of the actual plant, and measuring the yield of the cracked light oil at that time.

When determining kC0 _(T0) on the bench scale, it is preferable that the hydrogen partial pressure, hydrogen/feed oil ratio, LHSV, sulfur concentration in the feed oil, and metal concentration in the feed oil are set to conditions that correspond to the operating conditions of an actual plant.
Such hydrogen partial pressure is, for example, 5 to 18 MPa, the hydrogen/feedstock ratio is 170 to 1400 [Nm ³ /kL], the LHSV is 0.1 to 1.0 h ⁻¹ , the sulfur concentration in the feedstock is 1 to 5 mass %, and the metal concentration in the feedstock is 10 to 200 mass ppm.

kC0 _(T0) may be determined while carrying out the reaction in an actual plant as follows. It can be determined by substituting the amount of cracked light oil obtained and LHSV at the reaction temperature T _int immediately after the start of the reaction in the actual plant (after t _int days of reaction) into the above-mentioned formula 36. T _int is preferably 20 days or less, more preferably 10 days or less. When t _int is equal to or less than the above-mentioned upper limit, a value very close to the reaction rate constant of cracking of a fresh catalyst can be obtained. Note that T _int is a value determined in the above-mentioned reaction temperature calculation step from the degree of deterioration of the desulfurization reaction.

The activation energy _ED of decomposition can be calculated as follows:

When the activation energy E in the Arrhenius equation expressed by the above formula 6 is set as the activation energy _ED of decomposition and the natural logarithm of both sides is taken, the following formula 37 is obtained.

The cracking activation energy may be determined while the reaction is being carried out in an actual plant, or may be determined in advance on a bench scale based on the operating conditions of the actual plant. The hydrogen partial pressure, hydrogen/feedstock ratio, LHSV, and sulfur concentration in the feedstock are kept constant, and the reaction is carried out at a reaction temperature T(y'), and the amount of cracked light oil obtained in the product oil is measured. The reaction rate constant k is determined by substituting the obtained amount of cracked light oil and LHSV into Equation 32. The obtained reaction rate constant is substituted into Equation 37, and the result (lnk) on the left-hand side is plotted on the vertical axis and 1/T (1/T(y')) on the horizontal axis.

A similar reaction is carried out for y' types of reaction temperatures T(y'), and y' plots of the above are obtained. A regression line is drawn from the obtained plots, and its slope is determined. Since this slope is _ED /R, the activation energy of decomposition _ED can be determined by subtracting R from the slope.

The above y' is an integer of 3 or more. The larger the number of y', the more accurate _ED can be obtained. On the other hand, if the number of y' is too large, it takes a long time to obtain _ED , which is not efficient. In this embodiment, y' is preferably 3 to 20, and more preferably 3 to 10.

The hydrogen partial pressure, hydrogen/feed oil ratio, LHSV, sulfur concentration in the feed oil, and metal concentration in the feed oil used to determine _ED are preferably set to conditions that correspond to the operating conditions of an actual plant.
Such hydrogen partial pressure is, for example, 5 to 18 MPa, the hydrogen/feedstock ratio is 170 to 1400 [Nm ³ /kL], the LHSV is 0.1 to 1.0 h ⁻¹ , the sulfur concentration in the feedstock is 1 to 5 mass %, and the metal concentration in the feedstock is 10 to 200 mass ppm.
Similarly, it is preferable that the reaction temperature T(y') of the y' types is set to a condition that conforms to the operating conditions of the actual equipment. Such T(y') is 330 to 410°C.

By substituting the thus obtained k _C0(T0) , the decomposition activation energy E _D , T _SOR , and the reaction temperature T _t calculated in the reaction temperature calculation step described above into Equation 35, k _C0(Tt) is calculated.

<How to determine the degradation level of decomposition reaction>
When the desulfurization reaction activity of a catalyst decreases, the cracking reaction activity also decreases. Therefore, it is believed that there is a correlation between the degree of desulfurization reaction and the degree of decomposition reaction. The inventors of the present application focused on this correlation and discovered for the first time that the degree of decomposition reaction Φ _D can be calculated based on the above-mentioned degree of desulfurization reaction Φ. Below, we will explain how to calculate the degree of decomposition reaction Φ _D when using coke decomposition function 1 (or 1-1) and when using coke decomposition function 2 (or 2-1) as the decomposition reaction decomposition function.

(Method 1 for determining the degradation level of decomposition reaction)
Method 1 for determining Φ _D is a method for determining Φ _D using coke deterioration function 1 (or 1-1) in the deterioration function of the desulfurization reaction. Φ _D can be determined by the following equation 38.

Φ _D = βΦ _C Φ _M formula 38
In the above formula 38, Φ _D is the degradation degree of the cracking reaction, Φ _C is the coke degradation function 1 (or 1-1), Φ _M is the metal degradation function, and β is the cracking degradation coefficient (constant).

Since Φ _C and Φ _M can be determined by the above-mentioned method, once β is determined, Φ _D can be determined from Φ _C and Φ _M. In addition, in the above formula 38, Φ _D at the time when the reaction has elapsed is 0 is βΦ _C =1 (because the reaction has elapsed is 0, Φ _M =1).

In an actual plant or on a bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen/feed oil ratio, sulfur concentration in the feed oil, metal concentration in the feed oil, and sulfur concentration in the product oil are those of the assumed actual plant operating conditions. Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature. The reaction temperature at this time may be the reaction temperature _Tt calculated in the reaction temperature calculation step described above. Examples of assumed actual plant operating conditions include the conditions used to calculate the activation energy of cracking described above. The yield _Ct ' of cracked light oil after _t ' days of reaction is measured, and _ΦD is calculated by substituting the obtained Ct', _kC0(Tt) (kC0 _(Tt') ) calculated by the above method, and LHSV into Equation 29. Furthermore, _ΦC and _ΦM after t' days of reaction are calculated using the above method. _ΦD , _ΦC , and _ΦM are calculated in the same manner for multiple reactions after t' days. The combinations of Φ _D and Φ _C Φ _M obtained at the same reaction time are plotted with Φ _C Φ _M on the x-axis and Φ _D on the y-axis. A regression line is drawn between these plots (where x=0 and y=0 pass through). The slope of this line is β. The number of plots in determining β is preferably 10 to 100, more preferably 10 to 50. Furthermore, the above-mentioned t' in determining β is preferably after 3 days of reaction.

(Method 2 for determining the degradation level of decomposition reaction)
Method 2 for determining Φ _D is a method for determining Φ _D using coke deterioration function 2 (or 2-1) in the deterioration function of the desulfurization reaction. Φ _D can be determined by the following formula 39.

Φ _D = β ₁ Φ _M Φ ₁ + β ₂ Φ _M Φ ₂ Equation 39
In the formula 39, Φ _D is the degradation degree of the decomposition reaction, Φ _M is the metal degradation function, Φ ₁ is k ₁ ×exp(-D ₁ t) in the formula 13, Φ ₂ is k ₂ ×exp(-D ₂ t) in the formula 13, β ₁ is the decomposition degradation coefficient (constant) of the easily deactivated active species of the catalyst, and β ₂ is the decomposition degradation coefficient (constant) of the hardly deactivated active species of the catalyst. When the coke decomposition function 2-1 is used, k ₁ ×exp(-D ₁ 't) in the formula 17 is used as Φ ₁ , and k ₂ ×exp(-D ₂ 't) in the formula 17 is used as Φ ₂ .

Since Φ _M , Φ ₁ , and Φ ₂ can be determined by the above-mentioned method, once β ₁ and β ₂ are determined, Φ _D can be determined from Φ _M , Φ ₁ , and Φ _2. In addition, in the above formula 39, Φ _C at time 0 of reaction elapsed time is β ₁ Φ ₁ + β ₂ Φ ₂ = 1 (because the reaction elapsed time is 0, Φ _M = 1).

In an actual plant or on a bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen/feed oil ratio, sulfur concentration in the feed oil, metal concentration in the feed oil, and sulfur concentration in the product oil are those of the assumed actual plant operating conditions. Since the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature. The reaction temperature at this time may be the reaction temperature _Tt calculated in the reaction temperature calculation step described above. The amount Ct _' of cracked light oil obtained after _t ' days of reaction has elapsed is measured, and _ΦD is calculated by substituting the obtained Ct', _kC0(Tt) (kC0 _(Tt') ) calculated by the above method, and LHSV into Equation 29. Furthermore, _ΦM , _Φ1 , and _Φ2 after t' days of reaction have elapsed are calculated using the above method. The obtained _ΦD , _ΦM , _Φ1 , and _Φ2 are substituted into Equation 39. Similarly, Φ _Dn , Φ _Mn , Φ _1n , and Φ _2n are obtained after n number of reaction days t' have elapsed. If Equation 39 is satisfied for each combination, a simultaneous two-dimensional linear equation of Φ _Cn = β ₁ 'Φ _Mn Φ _1n + β ₂ 'Φ _Mn Φ _2n is obtained. In this equation, β ₁ ' and β ₂ ' with minimum error can be determined by two-dimensional linear regression with Φ Cn as the dependent variable and Φ _Mn Φ _1n and Φ _Mn Φ _2n as independent variables. The obtained β _{1 '} can be used as β ₁ in Equation 39, and the obtained β ₂ ' can be used as β ₂ in Equation 39. The number of combinations of Φ _C , Φ _M , Φ ₁ , and Φ ₂ in determining β ₁ and _β 2 is preferably 10 to 100, more preferably 10 to 50. In addition, the time t' for determining _β1 and _β2 is preferably after 3 days of reaction.

Using β or _β1 and _β2 obtained by the above method, _ΦD can be calculated from the above formula 38 or formula 39.

By substituting k _C0(Tt) obtained by the above-mentioned method, Φ _D obtained by the above-mentioned formula 38 or the above-mentioned formula 39, and LHSV into the above-mentioned formula 29, the yield of cracked light oil after any reaction time t days has elapsed can be calculated.

The ratio of the cracked light oil yield _Ct determined by the information processing method of this embodiment to the actually measured cracked light oil yield C _obs , C _t /C _obs , is preferably 0.80 to 1.20, more preferably 0.85 to 1.15, in mass %. When _{C t} /C _obs is within the above range, it can be determined that the cracked light oil yield has been estimated with high accuracy.

<Information output step>
The method may further include an information output step (S5 in FIG. 1) of outputting information indicating the yield of the cracked light oil thus obtained. For example, S5 is executed by the output unit 14.

<Hydrotreatment reaction of feedstock oil containing atmospheric distillation residue>
The hydrotreating reaction of feedstock oils containing atmospheric distillation residue will be outlined below.
Atmospheric distillation residue is a fraction having a boiling point range of 370°C or higher obtained by atmospheric distillation of crude oil. The density of atmospheric distillation residue is 0.92 to 1.00 g/mL. The content of atmospheric distillation residue in the feedstock oil may be, for example, 50% by volume or more, or 70% by volume or more.
An example of an oil type other than atmospheric distillation residue contained in the feedstock oil is vacuum distillation residue obtained by vacuum distilling atmospheric distillation residue. When the feedstock oil contains vacuum distillation residue, the content of vacuum distillation residue in the feedstock oil is, for example, 0 to 50% by volume.

The hydrotreating reaction of the feedstock containing atmospheric distillation residue can be carried out by contacting the feedstock containing atmospheric distillation residue with a hydrotreating catalyst in the presence of hydrogen.
The hydrotreating catalyst is not particularly limited, and any hydrotreating catalyst known in the art can be used. Various catalyst supports can be used, including, for example, silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, and the like, or mixtures of two or more of these. Among these inorganic oxides, preferred are alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia, with alumina being particularly preferred, and among aluminas, γ-alumina being particularly preferred. These inorganic oxides may be used alone or in combination of two or more.

The metal contained in the support as an active component is at least one metal selected from Group 6 and Groups 8-10 of the Periodic Table, preferably molybdenum, tungsten, cobalt, and nickel. These metals are effective in the metallic state, metal oxide, or metal sulfide form. They may also be bonded to the catalyst support by ion exchange or other methods. The content of this metal component is typically within the range of approximately 1-25 mass% of the catalyst, calculated as oxide. If the metal content is less than 1 mass%, the absolute amount of metal acting as active sites is low, preventing hydrotreating activity (hereinafter simply referred to as hydrotreating activity), including desulfurization activity. Conversely, if the supported metal content is greater than 25 mass%, metal aggregation occurs, reducing the number of active sites and, as a result, reducing hydrotreating activity. Furthermore, if necessary, phosphorus, boron, zinc, zirconia, etc. can be contained in addition to the active metals consisting of Groups 6 and 8 of the Periodic Table. When applying the method of the present invention, there are no restrictions on the form of the catalyst bed, and it can be applied to catalyst bed reactors such as fixed beds, moving beds, and fluidized beds.

The conditions for the hydrotreating reaction of feedstock containing atmospheric distillation residue are generally a reaction temperature of 330 to 410°C, preferably 360 to 400°C, a hydrogen partial pressure of 5 to 15 MPa, preferably 10 to 18 MPa, an LHSV of 0.1 to 1.0 h ^-1 , preferably 0.1 to 0.35 h ^-1 , and a hydrogen/feedstock ratio of 170 to 1400 [Nm ³ /kL], preferably 670 to 1200 [Nm ³ /kL].

The sulfur concentration in feedstock oils containing atmospheric distillation residue is typically 1 to 5 mass%. The sulfur concentration in the resulting oil is typically 0.1 to 0.5 mass%. The metal concentration in feedstock oils containing atmospheric distillation residue is typically 30 to 300 ppm by weight. The metal concentration in the resulting oil is typically 5 to 30 ppm by weight.

In this specification, the term "cracked light oil" cannot be generally defined as it differs depending on the feedstock oil, the equipment, etc., but examples thereof include fractions having a boiling point of 343°C or less and a carbon number of 5 or more. Note that components having a boiling point of 343°C or less and a carbon number of less than 5 are gas components, and therefore "cracked light oil" in this specification refers to, for example, fractions having a boiling point of 343°C or less.
The yield of cracked light oil can be determined by a method for measuring the yield of cracked light oil known in the art, for example, by calculating it from the proportion of fractions having a boiling point of 343°C or less using a distillation test such as ASTM D-6352.

≪Cracked light oil yield calculation device≫
The cracked light oil yield calculation device of this embodiment includes an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions a predetermined time after the start of the hydrotreating reaction of the feedstock containing atmospheric distillation residue; and a calculation unit that calculates the degradation levels of the desulfurization reaction and the cracking reaction of the catalyst using a degradation function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates the information about the feedstock, information about the product oil, and the reaction temperature required to satisfy the operating conditions based on the calculated degradation level of the desulfurization reaction of the catalyst, and calculates the cracked light oil yield based on the calculated reaction temperature and the degradation level of the cracking reaction of the catalyst.

The cracked light oil yield calculation device 1 of this embodiment is configured using an information processing device such as a personal computer, server device, or dedicated device. The cracked light oil yield calculation device 1 may be configured using one or more information processing devices. For example, the cracked light oil yield calculation device 1 may be configured as a cluster machine, a cloud, or in any other manner. Specifically, as shown in FIG. 2, the cracked light oil yield calculation device 1 has an acquisition unit 11 and a computer main body 12 that processes information from the acquisition unit. The cracked light oil yield calculation device 1 may also have an output unit 14 that outputs information processed in the computer main body 12 to the outside. These components are implemented, for example, by a hardware processor such as a CPU (Central Processing Unit) executing a program (software). Furthermore, some or all of these components may be implemented by hardware (including circuitry) such as an LSI (Large Scale Integrated circuit), ASIC (Application Specific Integrated Circuit), FPGA (Field-Programmable Gate Array), or GPU (Graphics Processing Unit), or by a combination of software and hardware. The program may be stored in advance in a storage device (a storage device with a non-transitory storage medium) such as an HDD (Hard Disk Drive) or flash memory, or may be stored in a removable storage medium (a non-transitory storage medium) such as a DVD or CD-ROM, and installed in the storage device by inserting the storage medium into a drive. The storage device may be configured, for example, with an HDD, flash memory, EEPROM (Electrically Erasable Programmable Read Only Memory), ROM (Read Only Memory), or RAM (Random Access Memory).

The acquisition unit 11 receives predetermined information input by the reaction operator and transmits the information acquired through this input to the computer main body 12. The information acquired by the acquisition unit 11 in this embodiment is, for the hydrotreating reaction of a feedstock containing atmospheric distillation residue oil, information on the feedstock oil a predetermined time after the start of the reaction, information on the product oil, and information on the operating conditions. The information on the feedstock oil a predetermined time after the start of the reaction, information on the product oil, and information on the operating conditions are as described above. For example, the acquisition unit 11 executes the information acquisition step described above. The acquisition unit 11 only needs to acquire information on the feedstock oil a predetermined time after the start of the reaction, information on the product oil, and information on the operating conditions, and there are no particular limitations on the acquisition method.

In this embodiment, the acquisition unit 11 is configured with a single keyboard. The specific configuration of the acquisition unit 11 is not limited, and although it is a keyboard in this embodiment, it may also be a touch panel or the like. It is also possible for acquisition units that acquire various types of information to be configured separately and each to be independently connected to the computer main body 12. The acquisition unit 11 may also be configured to directly acquire each of the above-mentioned information via wired or wireless connections from a computer or the like used for controlling the reactor, etc.

The computer main body 12 is, for example, a so-called computer capable of processing various types of information. The computer main body 12 includes an arithmetic unit 13. For example, a predetermined program is installed in the computer main body 12, and the execution of this program functionally configures the arithmetic unit 13. Specifically, the arithmetic unit 13 calculates the degree of degradation of the catalyst's desulfurization reaction and the degree of degradation of the cracking reaction using a degradation function based on the information on the feedstock oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit 11 at a predetermined time after the start of the reaction. Based on the calculated degree of degradation of the catalyst's desulfurization reaction, the computer calculates the reaction temperature required to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions. The yield of cracked light oil is calculated based on the calculated reaction temperature and the degree of degradation of the catalyst's cracking reaction. The degradation function is as described above. As described above, the reaction temperature can be determined, for example, from a degradation rate equation. Furthermore, the yield of cracked light oil can be determined, for example, from a cracked light oil yield function. For example, the calculation unit 13 executes the deterioration degree calculation step, reaction temperature calculation step, and cracked light oil yield calculation step described above. It is also preferable that the calculation unit 13 executes the step of determining the timing for switching η described above. The calculation unit 13 may include, for example, a processor such as a CPU (Central Processing Unit) or an MPU (Micro Processing Unit), and non-volatile or volatile semiconductor memory (e.g., RAM (Random Access Memory), ROM (Read Only Memory), flash memory, EPROM (Erasable Programmable Read Only Memory), or EEPROM (Electrically Erasable Programmable Read Only Memory)). For example, the calculation unit 13 may be a microcontroller such as an MCU.

The calculation unit 13 may output to the output unit 14 information regarding the feedstock oil obtained as described above, information regarding the product oil, and information indicating the amount of cracked light oil obtained at the reaction temperature required to satisfy the operating conditions.

The output unit 14 receives the calculation results (reaction temperatures) output by the computer main body 12 (more specifically, the calculation unit 13) and outputs the received calculation results to the outside. In this embodiment, the output unit 14 is configured as a display unit such as a CRT display, LCD display, or PDP, but is not limited to this and may be configured to output to a printing unit such as a printer, or to other devices (for example, a computer used to control the hydrotreating reaction of feedstock oil including atmospheric distillation residue oil). The output unit 14 may also be a combination of these. For example, the output unit 14 executes the information output step described above.

In addition, this embodiment provides a cracked light oil yield calculation program for causing a computer to function as a cracked light oil yield calculation device, and a non-transitory computer-readable recording medium storing the program. Examples of non-transitory computer-readable recording media include magnetic tape (such as digital data storage (DSS)), magnetic disks (such as hard disk drives (HDDs) and flexible disks (FDs)), optical disks (such as compact disks (CDs), digital versatile disks (DVDs), and Blu-ray disks (BDs)), magneto-optical disks (MOs), and flash memory (such as solid-state drives (SSDs), memory cards, and USB memory).

<Method of using the information processing method and the light cracked oil yield calculation device>
The information processing method and cracked light oil yield calculation device of this embodiment can estimate the yield of cracked light oil at the reaction temperature required to achieve specified reaction conditions for the hydrotreating reaction of feedstock oil containing atmospheric residue. The information processing method and cracked light oil yield calculation device of this embodiment can obtain a plot of estimated values of the yield of cracked light oil over time. Based on the relationship between the plot and the supply-demand balance between cracked light oil and residual heavy oil in the hydrotreating unit of atmospheric residue, the following applications are possible.

Utilization methods include estimating the reaction conditions (reaction temperature, throughput (LHSV)) required to obtain a specified yield of cracked light oil, estimating the yield of cracked light oil under specified reaction conditions (reaction temperature, throughput (LHSV)), and planning the production of cracked light oil and heavy oil by estimating and knowing the future yield of cracked light oil in advance. In other words, when a specified yield of cracked light oil is set for a specified operating time, Equation 29 becomes a function of kC0 _(Tt) , _ΦD , and LHSV. A combination of kC0 _(Tt) , _ΦD , and LHSV is found that satisfies the equation of Equation 29. From the reaction conditions in this combination, it is possible to obtain optimal yields of cracked light oil and heavy oil that correspond to the supply and demand balance. In determining the combination of kC0 _(Tt) , _ΦD , and LHSV that satisfies the equality of Equation 29, reaction conditions that can be changed include, for example, P, LHSV, S _F , and S _P. In such a utilization method, the acquisition unit 11 of the cracked light oil yield calculation device 1 acquires a predetermined cracked light oil yield, and the calculation unit 13 in the computer main body 12 calculates the combination of P, LHSV, S _F , and S _P that achieves the predetermined cracked light oil yield based on the cracked light oil yield calculation function, the degradation rate equation for the desulfurization reaction, the degradation function, etc.

The present invention will be explained in more detail below using examples, but the present invention is not limited to the following examples.

[Example 1]
On a bench scale, a hydrotreating reaction was carried out by contacting a feedstock containing 85% by volume of atmospheric distillation residue and 15% by volume of vacuum distillation residue with a hydrotreating catalyst. Based on the results obtained, the degradation function of the desulfurization reaction was calculated. In this example, the coke degradation function 2 represented by the above-mentioned formula 13 and the metal degradation function 1 represented by the above-mentioned formula 20 were used. When the parameters in the formulas 13 to 15 and 20 were determined by the above-mentioned method, k ₁ = 0.5, k ₂ = 0.5, α ₁ = 0.05, α ₂ = 0.0052, P _B = 13 (MPa), a = 2.6, Ec = 182 (kJ / mol), T _B = 643 (K), T _SOR = 633 (K), n = 2, η = 0.91, t _end = 411 days.

The reaction was carried out in an actual plant using the same feedstock and hydrotreating catalyst as in the bench-scale hydrotreating reaction. The operating conditions in Equations 13 to 15 were S _F = 3.27 (mass%), M _F = 41 (wt ppm), P = 10.3 (MPa), LHSV = 0.2 (h ^-1 ), S _P = 0.25 (mass%), and M _P = 11 (wt ppm).
Furthermore, the activation energy of desulfurization and the activation energy of decomposition were determined in advance by the above-mentioned method, and were found to be Ea = 147 (kJ/mol) and E _D = 180 (kJ/mol).

When k _C0(T0) was calculated from the measured value of the yield of cracked light oil at 1 day and time of reaction using Equation 36, it was 0.027 (h ^-1 ). The measured value of the reaction temperature at this time, _T0 , was 633 (K). Thereafter, in the early stage of the reaction, β 1 and β 2 were calculated from Equation 39 using Φ _M Φ ₁ (Φ ₁ = k ₁ × exp(-D ₁ t)) and Φ _M Φ ₂ (Φ ₂ = k ₂ × exp(-D ₂ t)) calculated from Equations 13 and 20, the measured value of the yield of cracked light oil, k _C0(T0) , and Φ _D calculated from Equation ₂₉ using LHSV, and the results were _{β 1 =} 1.1 and β ₂ = 0.8.

_ΦC and _ΦM obtained from the above parameters were substituted into Equation 2 to determine Φ. Note that η = 1 and _ΦM = 1 were set at the beginning of the reaction. When Z at (η switching timing 1) above reached 2°C or higher (243 days after reaction), _ΦM was set to the _ΦM determined from Equation 20, and the reaction was continued. Φ, Ea, and T _SOR obtained in this manner were substituted into Equation 26 to determine the required temperature _Tt after any t days of reaction. Furthermore, kC0(Tt) was determined from the obtained required temperature _Tt and kC0 _(T0) , and kC0( _{Tt )} , _ΦD , and LHSV were substituted into Equation 29 to determine the yield _Ct of light cracked oil after any t days of reaction. The results are shown in Table 1.

The actual measured values for the yield of cracked light oil in Table 1 were analyzed as follows: The product oil was distilled and separated into a fraction with a boiling point of 343°C or less and a fraction with a boiling point above 343°C. The fraction with a boiling point of 343°C or less was then divided by the amount (mass) of the product oil before distillation and multiplied by 100 to calculate the yield.

As shown in Table 1, it was found that the yield of cracked light oil _Ct determined by the present invention was almost equal to the actually measured value of the yield of cracked light oil.

1...Cracked light oil yield calculation device 11...Acquisition section 12...Computer main body 13...Calculation section 14...Output section

Claims (10)

With respect to the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue oil, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of the reaction;
a deterioration degree calculation step of calculating a deterioration degree of a desulfurization reaction and a deterioration degree of a cracking reaction of the catalyst using a deterioration function based on the acquired information on the feedstock oil, the information on the product oil, and the information on the operating conditions;
a reaction temperature calculation step of calculating information about the feed oil, information about the product oil, and a reaction temperature necessary to satisfy the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst;
and a cracked light oil yield calculation step of calculating the cracked light oil yield based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst ,
the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil and may include information about a metal concentration; the information about the product oil includes information about the sulfur concentration in the product oil and may include information about a metal concentration; the information about the operating conditions includes information about a hydrogen partial pressure, information about a catalyst loading amount, and information about a feedstock oil supply amount;
The degradation function is a function expressed by the following equation 2:
The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 38:
The amount of cracked light oil obtained is calculated by the following formula 29.
Φ = Φ _C Φ _M Equation 2
In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, Φ _C is the coke deterioration function represented by the following formula 3, and Φ _M is the metal deterioration function.
Φ _C =exp(-Dt) Equation 3
In the above formula 3, D is a deterioration coefficient due to coke, an active species in the desulfurization reaction of the catalyst, and is calculated using the following formula 4, and t is the number of days elapsed since the reaction began.
In the above formula 4, α is the catalyst constant of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst), S _F is the sulfur concentration (mass%) in the feedstock oil after t days of reaction, S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, LHSV is the liquid hourly space velocity (h ^-1 ) after t days of reaction, P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is a gas constant: 0.00831 (kJ / (mol · K)), T _B is the reference reaction temperature (K), and T _SOR is the required temperature on day 0 (K). α, P _B , a, Ec, T _B , and T _SOR are constants determined depending on the catalyst used. These constants are determined while carrying out the reaction in an actual reactor, or are determined in advance on a bench scale based on the operating conditions of the actual reactor.
Φ _D = βΦ _C Φ _M formula 38
In Equation 38, Φ _D is the degree of decomposition reaction of the catalyst, Φ _C is a coke decomposition function, Φ _M is a metal decomposition function, and β is a decomposition decomposition coefficient (constant). β is determined while the reaction is being carried out in an actual plant, or is determined in advance on a bench scale based on the operating conditions of the actual plant.
In the above equation 29, C _t is the yield (mass%) of cracked light oil after t days of reaction, k _C0(Tt) is the reaction rate constant (h ⁻¹ ) of the cracking reaction at the reaction temperature T _t calculated in the reaction temperature calculation step for the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ _D is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h ⁻¹ ) after t days of reaction . With respect to the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue oil, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of the reaction;
a deterioration degree calculation step of calculating a deterioration degree of a desulfurization reaction and a deterioration degree of a cracking reaction of the catalyst using a deterioration function based on the acquired information on the feedstock oil, the information on the product oil, and the information on the operating conditions;
a reaction temperature calculation step of calculating information about the feed oil, information about the product oil, and a reaction temperature necessary to satisfy the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst;
and a cracked light oil yield calculation step of calculating the cracked light oil yield based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst,
The information on the feedstock oil includes information on the sulfur concentration in the feedstock oil and may include information on a metal concentration, the information on the product oil includes information on the sulfur concentration in the product oil and may include information on a metal concentration, the information on the operating conditions includes information on the hydrogen partial pressure, information on the hydrogen supply amount, information on the catalyst loading amount, and information on the feedstock oil supply amount,
The degradation function is expressed by the following equation 2:
The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 38:
The amount of cracked light oil obtained is calculated by the following formula 29.
Φ＝Φ _C Φ _M Formula 2
In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, and Φ _C is the coke deterioration function expressed by the following equation 10, and Φ _M is the metal degradation function.
Φ _C =exp(-D’t) Formula 10
In the above formula 10, D' is the deterioration coefficient of coke, which is an active species in the desulfurization reaction of the catalyst, and is calculated using the following formula 11, and t is the number of days elapsed since the reaction began.
In the above formula 11, α' is a catalytic constant of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the coke in the catalyst), and S _F is the sulfur concentration (mass%) in the feed oil after any reaction time t days, and S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, and LHSV is the liquid hourly space velocity (h ^-1 ) and P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, and G _B is the standard hydrogen/feed oil ratio (Nm ³ /kL), G is the hydrogen/feedstock ratio (Nm ³ /kL), b is the hydrogen/feed oil ratio coefficient, Ec is the activation energy of coke deterioration (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), and T _B is the reference reaction temperature (K), and T _SOR is the required temperature (K) on day 0. _B , a, G _B ,b,Ec,T _B , T _SOR is a constant determined depending on the catalyst used. The constant is determined while carrying out a reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
Φ _D ＝βΦ _C Φ _M Formula 38
In the above formula 38, Φ _D is the degradation rate of the catalyst decomposition reaction, and Φ _C is the coke degradation function, and Φ _M is a metal deterioration function, and β is a decomposition deterioration coefficient (constant). β is determined while carrying out a reaction in an actual plant, or is determined in advance on a bench scale based on the operating conditions of the actual plant.
In the formula 29, C _t is the yield of light cracked oil (mass%) after any reaction t days, and k _C0(Tt) is the reaction temperature T calculated in the reaction temperature calculation step of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction). _t The reaction rate constant of the decomposition reaction (h ^-1 ) and Φ _D is the degree of deterioration of the catalyst decomposition reaction, and LHSV is the liquid hourly space velocity (h ^-1 ) With respect to the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue oil, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of the reaction;
a deterioration degree calculation step of calculating a deterioration degree of a desulfurization reaction and a deterioration degree of a cracking reaction of the catalyst using a deterioration function based on the acquired information on the feedstock oil, the information on the product oil, and the information on the operating conditions;
a reaction temperature calculation step of calculating information about the feed oil, information about the product oil, and a reaction temperature necessary to satisfy the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst;
and a cracked light oil yield calculation step of calculating the cracked light oil yield based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst,
the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil and may include information about a metal concentration; the information about the product oil includes information about the sulfur concentration in the product oil and may include information about a metal concentration; the information about the operating conditions includes information about a hydrogen partial pressure, information about a catalyst loading amount, and information about a feedstock oil supply amount;
The degradation function is a function expressed by the following equation 2:
The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 39:
The amount of cracked light oil obtained is calculated by the following formula 29.
Φ＝Φ _C Φ _M Formula 2
In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, and Φ _C is the coke deterioration function expressed by the following equation 13, and Φ _M is the metal degradation function.
Φ _C = k ₁ ×exp(-D ₁ t) + k ₂ ×exp(-D ₂ t) Equation 13
In the formula 13, k ₁ is the active site coefficient of the easily deactivated active species of the catalyst for desulfurization reaction, and k ₂ is the active site coefficient of the active species that is difficult to deactivate in the desulfurization reaction of the catalyst, and the active site coefficient represents the relative reaction rate constant of the desulfurization reaction of both active species. ₁ is the deterioration coefficient of the catalyst due to coke, an easily deactivated active species in the desulfurization reaction, and is calculated using the following formula 14: ₂ is the deterioration coefficient due to coke, an active species that is difficult to deactivate in the desulfurization reaction of the catalyst, and is calculated using the following formula 15, t is the number of days elapsed since the reaction (days), and k ₁ +k ₂ = 1, and k ₁ and k ₂ is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
In the formula 14 and the formula 15, S _F is the sulfur concentration (mass%) in the feed oil after any reaction time t days, and S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, and LHSV is the liquid hourly space velocity (h ^-1 ) and P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), and T _B is the reference reaction temperature (K), and T _SOR is the required temperature (K) on day 0. In the above formula 14, α ₁ is a catalytic constant of the easily deactivated active site of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst), and in the above formula 15, α ₂ is the catalytic constant of the desulfurization reaction's refractory active site (a constant that represents the rate of deterioration of the desulfurization reaction due to coke on the catalyst). ₁ , α ₂ , P _B , a, Ec, T _B , T _SOR is a constant determined depending on the catalyst used. The above constant is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
Φ _D = β ₁ Φ _M Φ ₁ +β ₂ Φ _M Φ ₂ Formula 39
In the formula 39, Φ _D is the degradation rate of the catalyst decomposition reaction, and Φ _M is the metal degradation function, and Φ ₁ is k in the above formula 13 ₁ ×exp(-D ₁ t), and Φ ₂ is k in the above formula 13 ₂ ×exp(-D ₂ t), and β ₁ is the decomposition deterioration coefficient (constant) of the easily deactivated active species of the catalyst, and β ₂ is the decomposition degradation coefficient (constant) of the catalyst's resistant to deactivation. ₁ and β ₂ is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
In the formula 29, C _t is the yield of light cracked oil (mass%) after any reaction t days, and k _C0(Tt) is the reaction temperature T calculated in the reaction temperature calculation step of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction). _t The reaction rate constant of the decomposition reaction (h ^-1 ) and Φ _D is the degree of deterioration of the catalyst decomposition reaction, and LHSV is the liquid hourly space velocity (h ^-1 ) With respect to the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue oil, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of the reaction;
a deterioration degree calculation step of calculating a deterioration degree of a desulfurization reaction and a deterioration degree of a cracking reaction of the catalyst using a deterioration function based on the acquired information on the feedstock oil, the information on the product oil, and the information on the operating conditions;
a reaction temperature calculation step of calculating information about the feed oil, information about the product oil, and a reaction temperature necessary to satisfy the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst;
and a cracked light oil yield calculation step of calculating the cracked light oil yield based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst,
The information about the feedstock oil includes information about the sulfur concentration in the feedstock oil and may include information about a metal concentration, the information about the product oil includes information about the sulfur concentration in the product oil and may include information about a metal concentration, and the information about the operating conditions includes information about the hydrogen partial pressure, information about the hydrogen supply amount, information about the catalyst loading amount, and information about the feedstock oil supply amount,
The degradation function is expressed by the following equation 2:
The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 39:
The amount of cracked light oil obtained is calculated by the following formula 29.
Φ＝Φ _C Φ _M Formula 2
In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, and Φ _C is the coke deterioration function expressed by the following equation 17, and Φ _M is the metal degradation function.
Φ _C = k ₁ ×exp(-D ₁ 't) + k ₂ ×exp(-D ₂ 't) Equation 17
In the formula 17, k ₁ is the active site coefficient of the easily deactivated active species of the catalyst for desulfurization reaction, and k ₂ is the active site coefficient of the active species that is difficult to deactivate in the desulfurization reaction of the catalyst, and the active site coefficient represents the relative reaction rate constant of the desulfurization reaction of both active species. ₁ ' is the deterioration coefficient of coke, an easily deactivated active species in the desulfurization reaction of the catalyst, and is calculated using the following formula 18. ₂ ' is the deterioration coefficient of coke, an active species that is difficult to deactivate in the desulfurization reaction of the catalyst, and is calculated using the following formula 19, t is the number of days elapsed since the reaction (days), and k ₁ +k ₂ = 1, and k ₁ and k ₂ is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
In the formula 18 and the formula 19, S _F is the sulfur concentration (mass%) in the feed oil after any reaction time t days, and S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, and LHSV is the liquid hourly space velocity (h ^-1 ) and P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, and G _B is the standard hydrogen/feed oil ratio (Nm ³ /kL), G is the hydrogen/feedstock ratio (Nm ³ /kL), b is the hydrogen/feed oil ratio coefficient, Ec is the activation energy of coke deterioration (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), and T _B is the reference reaction temperature (K), and T _SOR is the required temperature (K) on day 0. In the above formula 18, α ₁ ' is a catalytic constant of the easily deactivated active site of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst), and in the above formula 19, α ₂ ' is the catalytic constant of the deactivation-resistant active site of the desulfurization reaction (a constant representing the rate of deterioration of the desulfurization reaction due to coke on the catalyst). ₁ ', α ₂ ', P _B , a, G _B ,b,Ec,T _B , T _SOR is a constant determined depending on the catalyst used. The above constant is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
Φ _D = β ₁ Φ _M Φ ₁ +β ₂ Φ _M Φ ₂ Formula 39
In the formula 39, Φ _D is the degradation rate of the catalyst decomposition reaction, and Φ _M is the metal degradation function, and Φ ₁ is k in the above formula 17 ₁ ×exp(-D ₁ 't), and Φ ₂ is k in the above formula 17 ₂ ×exp(-D ₂ 't), and β ₁ is the decomposition deterioration coefficient (constant) of the easily deactivated active species of the catalyst, and β ₂ is the decomposition degradation coefficient (constant) of the catalyst's resistant to deactivation. ₁ and β ₂ is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
In the formula 29, C _t is the yield of light cracked oil (mass%) after any reaction t days, and k _C0(Tt) is the reaction temperature T calculated in the reaction temperature calculation step of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction). _t The reaction rate constant of the decomposition reaction (h ^-1 ) and Φ _D is the degree of deterioration of the catalyst decomposition reaction, and LHSV is the liquid hourly space velocity (h ^-1 ) 1. A cracked light oil yield calculation device comprising: an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions at a predetermined time after the start of a hydrotreating reaction of a feedstock containing atmospheric distillation residue; and a calculation unit that calculates a deterioration level of a desulfurization reaction and a deterioration level of a cracking reaction of a catalyst using a deterioration function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates a reaction temperature necessary to satisfy the information about the feedstock, information about the product oil, and the operating conditions based on the calculated deterioration level of the desulfurization reaction of the catalyst, and calculates a cracked light oil yield based on the calculated reaction temperature and the deterioration level of the cracking reaction of the catalyst ,
the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil and may include information about a metal concentration; the information about the product oil includes information about the sulfur concentration in the product oil and may include information about a metal concentration; the information about the operating conditions includes information about a hydrogen partial pressure, information about a catalyst loading amount, and information about a feedstock oil supply amount;
The degradation function is a function expressed by the following equation 2:
The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 38:
The amount of cracked light oil obtained is calculated by the following equation 29.
Φ = Φ _C Φ _M Equation 2
In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, Φ _C is the coke deterioration function represented by the following formula 3, and Φ _M is the metal deterioration function.
Φ _C =exp(-Dt) Equation 3
In the above formula 3, D is a deterioration coefficient due to coke, an active species in the desulfurization reaction of the catalyst, and is calculated using the following formula 4, and t is the number of days elapsed since the reaction began.
In the above formula 4, α is the catalyst constant of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst), S _F is the sulfur concentration (mass%) in the feedstock oil after t days of reaction, S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, LHSV is the liquid hourly space velocity (h ^-1 ) after t days of reaction, P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is a gas constant: 0.00831 (kJ / (mol · K)), T _B is the reference reaction temperature (K), and T _SOR is the required temperature on day 0 (K). α, P _B , a, Ec, T _B , and T _SOR are constants determined depending on the catalyst used. These constants are determined while carrying out the reaction in an actual reactor, or are determined in advance on a bench scale based on the operating conditions of the actual reactor.
Φ _D = βΦ _C Φ _M formula 38
In Equation 38, Φ _D is the degree of decomposition reaction of the catalyst, Φ _C is a coke decomposition function, Φ _M is a metal decomposition function, and β is a decomposition decomposition coefficient (constant). β is determined while the reaction is being carried out in an actual plant, or is determined in advance on a bench scale based on the operating conditions of the actual plant.
In the above equation 29, C _t is the yield (mass%) of cracked light oil after t days of reaction, k _C0(Tt) is the reaction rate constant (h ⁻¹ ) of the cracking reaction at the calculated reaction temperature T _t of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction) , Φ _D is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h ⁻¹ ) after t days of reaction . 1. A cracked light oil yield calculation device comprising: an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions at a predetermined time after the start of a hydrotreating reaction of a feedstock containing atmospheric distillation residue; and a calculation unit that calculates a deterioration level of a desulfurization reaction and a deterioration level of a cracking reaction of a catalyst using a deterioration function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates a reaction temperature necessary to satisfy the information about the feedstock, information about the product oil, and the operating conditions based on the calculated deterioration level of the desulfurization reaction of the catalyst, and calculates a cracked light oil yield based on the calculated reaction temperature and the deterioration level of the cracking reaction of the catalyst,
The information on the feedstock oil includes information on the sulfur concentration in the feedstock oil and may include information on a metal concentration, the information on the product oil includes information on the sulfur concentration in the product oil and may include information on a metal concentration, the information on the operating conditions includes information on the hydrogen partial pressure, information on the hydrogen supply amount, information on the catalyst loading amount, and information on the feedstock oil supply amount,
The degradation function is expressed by the following equation 2:
The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 38:
The amount of cracked light oil obtained is calculated by the following equation 29.
Φ＝Φ _C Φ _M Formula 2
In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, and Φ _C is the coke deterioration function expressed by the following equation 10, and Φ _M is the metal degradation function.
Φ _C =exp(-D’t) Formula 10
In the above formula 10, D' is the deterioration coefficient of coke, which is an active species in the desulfurization reaction of the catalyst, and is calculated using the following formula 11, and t is the number of days elapsed since the reaction began.
In the above formula 11, α' is a catalytic constant of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the coke in the catalyst), and S _F is the sulfur concentration (mass%) in the feed oil after any reaction time t days, and S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, and LHSV is the liquid hourly space velocity (h ^-1 ) and P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, and G _B is the standard hydrogen/feed oil ratio (Nm ³ /kL), G is the hydrogen/feedstock ratio (Nm ³ /kL), b is the hydrogen/feed oil ratio coefficient, Ec is the activation energy of coke deterioration (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), and T _B is the reference reaction temperature (K), and T _SOR is the required temperature (K) on day 0. _B , a, G _B ,b,Ec,T _B , T _SOR is a constant determined depending on the catalyst used. The constant is determined while carrying out a reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
Φ _D ＝βΦ _C Φ _M Formula 38
In the formula 38, Φ _D is the degradation rate of the catalyst decomposition reaction, and Φ _C is the coke degradation function, and Φ _M is a metal deterioration function, and β is a decomposition deterioration coefficient (constant). β is determined while carrying out a reaction in an actual plant, or is determined in advance on a bench scale based on the operating conditions of the actual plant.
In the formula 29, C _t is the yield of light cracked oil (mass%) after any reaction t days, and k _C0(Tt) is the calculated reaction temperature T of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction). _t The reaction rate constant of the decomposition reaction (h ^-1 ) and Φ _D is the degree of deterioration of the catalyst decomposition reaction, and LHSV is the liquid hourly space velocity (h ^-1 ) 1. A cracked light oil yield calculation device comprising: an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions at a predetermined time after the start of a hydrotreating reaction of a feedstock containing atmospheric distillation residue; and a calculation unit that calculates a deterioration level of a desulfurization reaction and a deterioration level of a cracking reaction of a catalyst using a deterioration function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates a reaction temperature necessary to satisfy the information about the feedstock, information about the product oil, and the operating conditions based on the calculated deterioration level of the desulfurization reaction of the catalyst, and calculates a cracked light oil yield based on the calculated reaction temperature and the deterioration level of the cracking reaction of the catalyst,
the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil and may include information about a metal concentration; the information about the product oil includes information about the sulfur concentration in the product oil and may include information about a metal concentration; the information about the operating conditions includes information about a hydrogen partial pressure, information about a catalyst loading amount, and information about a feedstock oil supply amount;
The degradation function is a function expressed by the following equation 2:
The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 39:
The amount of cracked light oil obtained is calculated by the following equation 29.
Φ＝Φ _C Φ _M Formula 2
In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, and Φ _C is the coke deterioration function expressed by the following equation 13, and Φ _M is the metal degradation function.
Φ _C = k ₁ ×exp(-D ₁ t) + k ₂ ×exp(-D ₂ t) Equation 13
In the formula 13, k ₁ is the active site coefficient of the easily deactivated active species of the catalyst for desulfurization reaction, and k ₂ is the active site coefficient of the active species that is difficult to deactivate in the desulfurization reaction of the catalyst, and the active site coefficient represents the relative reaction rate constant of the desulfurization reaction of both active species. ₁ is the deterioration coefficient of the catalyst due to coke, an easily deactivated active species in the desulfurization reaction, and is calculated using the following formula 14: ₂ is the deterioration coefficient due to coke, an active species that is difficult to deactivate in the desulfurization reaction of the catalyst, and is calculated using the following formula 15, t is the number of days elapsed since the reaction (days), and k ₁ +k ₂ = 1, and k ₁ and k ₂ is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
In the formula 14 and the formula 15, S _F is the sulfur concentration (mass%) in the feed oil after any reaction time t days, and S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, and LHSV is the liquid hourly space velocity (h ^-1 ) and P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), and T _B is the reference reaction temperature (K), and T _SOR is the required temperature (K) on day 0. In the above formula 14, α ₁ is a catalytic constant of the easily deactivated active site of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst), and in the above formula 15, α ₂ is the catalytic constant of the desulfurization reaction's refractory active site (a constant that represents the rate of deterioration of the desulfurization reaction due to coke on the catalyst). ₁ , α ₂ , P _B , a, Ec, T _B , T _SOR is a constant determined depending on the catalyst used. The above constant is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
Φ _D = β ₁ Φ _M Φ ₁ +β ₂ Φ _M Φ ₂ Formula 39
In the formula 39, Φ _D is the degradation rate of the catalyst decomposition reaction, and Φ _M is the metal degradation function, and Φ ₁ is k in the above formula 13 ₁ ×exp(-D ₁ t), and Φ ₂ is k in the above formula 13 ₂ ×exp(-D ₂ t), and β ₁ is the decomposition deterioration coefficient (constant) of the easily deactivated active species of the catalyst, and β ₂ is the decomposition degradation coefficient (constant) of the catalyst's resistant to deactivation. ₁ and β ₂ is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
In the formula 29, C _t is the yield of light cracked oil (mass%) after any reaction t days, and k _C0(Tt) is the calculated reaction temperature T of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction). _t The reaction rate constant of the decomposition reaction (h ^-1 ) and Φ _D is the degree of deterioration of the catalyst decomposition reaction, and LHSV is the liquid hourly space velocity (h ^-1 ) 1. A cracked light oil yield calculation device comprising: an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions at a predetermined time after the start of a hydrotreating reaction of a feedstock containing atmospheric distillation residue; and a calculation unit that calculates a deterioration level of a desulfurization reaction and a deterioration level of a cracking reaction of a catalyst using a deterioration function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates a reaction temperature necessary to satisfy the information about the feedstock, information about the product oil, and the operating conditions based on the calculated deterioration level of the desulfurization reaction of the catalyst, and calculates a cracked light oil yield based on the calculated reaction temperature and the deterioration level of the cracking reaction of the catalyst,
The information on the feedstock oil includes information on the sulfur concentration in the feedstock oil and may include information on a metal concentration, the information on the product oil includes information on the sulfur concentration in the product oil and may include information on a metal concentration, the information on the operating conditions includes information on the hydrogen partial pressure, information on the hydrogen supply amount, information on the catalyst loading amount, and information on the feedstock oil supply amount,
The degradation function is expressed by the following equation 2:
The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 39:
The amount of cracked light oil obtained is calculated by the following equation 29.
Φ＝Φ _C Φ _M Formula 2
In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, and Φ _C is the coke deterioration function expressed by the following equation 17, and Φ _M is the metal degradation function.
Φ _C = k ₁ ×exp(-D ₁ 't) + k ₂ ×exp(-D ₂ 't) Equation 17
In the formula 17, k ₁ is the active site coefficient of the easily deactivated active species of the catalyst for desulfurization reaction, and k ₂ is the active site coefficient of the active species that is difficult to deactivate in the desulfurization reaction of the catalyst, and the active site coefficient represents the relative reaction rate constant of the desulfurization reaction of both active species. ₁ ' is the deterioration coefficient of coke, an easily deactivated active species in the desulfurization reaction of the catalyst, and is calculated using the following formula 18. ₂ ' is the deterioration coefficient of coke, an active species that is difficult to deactivate in the desulfurization reaction of the catalyst, and is calculated using the following formula 19, t is the number of days elapsed since the reaction (days), and k ₁ +k ₂ = 1, and k ₁ and k ₂ is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
In the formula 18 and the formula 19, S _F is the sulfur concentration (mass%) in the feed oil after any reaction time t days, and S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, and LHSV is the liquid hourly space velocity (h ^-1 ) and P _B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, and G _B is the standard hydrogen/feed oil ratio (Nm ³ /kL), G is the hydrogen/feedstock ratio (Nm ³ /kL), b is the hydrogen/feed oil ratio coefficient, Ec is the activation energy of coke deterioration (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), and T _B is the reference reaction temperature (K), and T _SOR is the required temperature (K) on day 0. In the above formula 18, α ₁ ' is a catalytic constant of the easily deactivated active site of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction due to coke on the catalyst), and in the above formula 19, α ₂ ' is the catalytic constant of the deactivation-resistant active site of the desulfurization reaction (a constant representing the rate of deterioration of the desulfurization reaction due to coke on the catalyst). ₁ ', α ₂ ', P _B , a, G _B ,b,Ec,T _B , T _SOR is a constant determined depending on the catalyst used. The above constant is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
Φ _D = β ₁ Φ _M Φ ₁ +β ₂ Φ _M Φ ₂ Formula 39
In the formula 39, Φ _D is the degradation rate of the catalyst decomposition reaction, and Φ _M is the metal degradation function, and Φ ₁ is k in the above formula 17 ₁ ×exp(-D ₁ 't), and Φ ₂ is k in the above formula 17 ₂ ×exp(-D ₂ 't), and β ₁ is the decomposition deterioration coefficient (constant) of the easily deactivated active species of the catalyst, and β ₂ is the decomposition degradation coefficient (constant) of the catalyst's resistant to deactivation. ₁ and β ₂ is determined while carrying out the reaction in an actual reactor, or is determined in advance on a bench scale based on the operating conditions of the actual reactor.
In the formula 29, C _t is the yield of light cracked oil (mass%) after any reaction t days, and k _C0(Tt) is the calculated reaction temperature T of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction). _t The reaction rate constant of the decomposition reaction (h ^-1 ) and Φ _D is the degree of deterioration of the catalyst decomposition reaction, and LHSV is the liquid hourly space velocity (h ^-1 ) A program for calculating the yield of cracked light oil that causes a computer to function as the cracked light oil yield calculation device described in any one of claims 5 to 8. A non-transitory computer-readable recording medium storing the program described in claim 9.