Information processing method, reaction temperature calculation device, reaction temperature calculation program, and non-transitory computer readable recording medium

Abstract

To provide, regarding hydrotreating reaction of raw oil including atmospheric distillation residue kerosene, an information processing method capable of estimating a reaction temperature required to achieve a predetermined reaction condition, a reaction temperature calculation device capable of estimating the reaction temperature, a reaction temperature calculation program for forcing a computer to function as the reaction temperature calculation device, and a non-temporary readable recording medium for the computer that stores the program.SOLUTION: An information processing method includes: an information acquisition step to acquire information on raw oil including atmospheric distillation kerosene when a predetermined time has passed since start of reaction, information on product oil and information on an operation condition; a deterioration level calculation step to calculate the deterioration level of a catalyst by a deterioration function on the basis of the acquired information; and a reaction temperature calculation step to calculate a reaction temperature required to satisfy the information on raw oil, the information on product oil, and the operation condition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an information processing method, a reaction temperature calculation device, a reaction temperature calculation program, and a non-transitory computer-readable recording medium. [Background technology]

[0002] Kerosene base stock is produced by hydrotreating atmospheric kerosene obtained by atmospheric distillation of crude oil. Hydrotreating is carried out by contacting atmospheric kerosene with a hydrotreating catalyst in the presence of hydrogen.

[0003] In hydrotreating, coke is produced as a by-product, and the activity of the hydrotreating catalyst decreases over time as the coke accumulates on the catalyst. Therefore, in order to keep the sulfur content in the product oil below a certain level, the reaction temperature must be increased to counter the decrease in activity of the hydrotreating catalyst.

[0004] When setting this reaction temperature, if the reaction temperature is too high, the catalyst activity will decrease, making it impossible to achieve the specified operation time (number of days), and productivity will decrease. On the other hand, if the reaction temperature is too low, the catalyst activity decrease will be mitigated, and excess capacity will be generated before the specified operation time, and if the excess capacity cannot be utilized, productivity will decrease. Therefore, a method for accurately estimating the specified reaction conditions (temperature, processing amount) is desired.

[0005] In the field of crude oil refining, various methods for accurately estimating the optimal reaction temperature have been studied. For example, Patent Document 1 discloses a method for estimating the reaction temperature required after switching in the hydrotreatment of a feedstock containing atmospheric distillation light oil, when the feedstock is switched to a feedstock containing atmospheric distillation light oil with different properties, from information on the properties of the atmospheric distillation light oil before switching and operating conditions, and information on the properties of the atmospheric distillation light oil after switching and operating conditions other than the reaction temperature. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 10-60455 Summary of the Invention [Problem to be solved by the invention]

[0007] The method for estimating the reaction temperature described in Patent Document 1 focuses on the properties of the feedstock oil, and does not consider the activity reduction of the hydrotreating catalyst. Therefore, a method for estimating the optimal reaction temperature while taking into account the activity reduction of the hydrotreating catalyst is desired.

[0008] The present invention has been made in consideration of the above circumstances, and has an objective of providing an information processing method capable of estimating a reaction temperature necessary to achieve specified reaction conditions for a hydrotreating reaction of a feedstock oil including atmospheric distillation kerosene, a reaction temperature calculation device capable of estimating the reaction temperature, a reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device, and a non-transitory readable recording medium for a computer having the program stored therein. [Means for solving the problem]

[0009] 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 oil including atmospheric distilled kerosene, comprising: 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 catalyst using a deterioration function based on the acquired information on the feedstock oil, information on the product oil, and information on the operating conditions; and a reaction temperature calculation step of calculating a reaction temperature required to satisfy the information on the feedstock oil, information on the product oil, and the operating conditions based on the deterioration degree of the catalyst. [2] The information processing method according to [1], wherein the deterioration function is a coke deterioration function relating to deterioration of a catalyst due to coke deposition. [3] The information processing method according to [1] or [2], wherein the information relating to the feedstock oil includes information relating to the sulfur concentration in the feedstock oil, and the information relating to the produced oil includes information relating to the sulfur concentration in the produced oil. [4] The information processing method according to any one of [1] to [3], wherein the information on the operating conditions includes information on hydrogen partial pressure, information on catalyst loading amount, and information on the feedstock supply amount. [5] A reaction temperature calculation device comprising: an acquisition unit that acquires information regarding the feedstock oil, information regarding the product oil, and information regarding operating conditions at a predetermined time after the start of the reaction, regarding a hydrotreating reaction of a feedstock oil including atmospheric distilled kerosene; and a calculation unit that calculates a degree of catalyst deterioration using a deterioration function based on the information regarding the feedstock oil, the information regarding the product oil, and the information regarding the operating conditions acquired by the acquisition unit, and calculates a reaction temperature required to satisfy the information regarding the feedstock oil, the information regarding the product oil, and the operating conditions based on the calculated degree of catalyst deterioration. [6] The reaction temperature calculation device according to [5], wherein the deterioration function is a coke deterioration function relating to deterioration of the catalyst due to coke deposition. [7] The reaction temperature calculation device described in [5] or [6], wherein the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil, and the information about the produced oil includes information about the sulfur concentration in the produced oil. [8] The reaction temperature 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 supply amount. [9] A reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device according to any one of [5] to [8].

[10] A non-transitory computer-readable recording medium storing the program described in [9]. Effect of the Invention

[0010] According to the present invention, there can be provided an information processing method capable of estimating a reaction temperature necessary to achieve specified reaction conditions for a hydrotreating reaction of a feedstock oil including atmospheric distillation kerosene, a reaction temperature calculation device capable of estimating the reaction temperature, a reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device, and a non-transitory readable recording medium for a computer having the program stored therein. [Brief description of the drawings]

[0011] [Figure 1] 1 is a flowchart of an information processing method according to an embodiment. [Diagram 2] 1 is a flowchart of an information processing method according to an embodiment. [Diagram 3] 1 is a flowchart of an information processing method according to an embodiment. [Figure 4] FIG. 1 is a configuration block diagram of a reaction temperature calculation device according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The following describes in detail the embodiments of the present invention. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to these contents and can be modified and implemented within the scope of its gist.

[0013] <Information processing method> The information processing method of this embodiment includes an information acquisition step (S1 in FIG. 1) for acquiring information on the feedstock oil, information on the product oil, and information on the operating conditions at a predetermined time after the start of the reaction, regarding the hydrotreating reaction of the feedstock oil including atmospheric distillation kerosene, a deterioration degree calculation step (S2 in FIG. 1) for calculating the deterioration degree of the catalyst by a deterioration function based on the acquired information on the feedstock oil, information on the product oil, and information on the operating conditions, and a reaction temperature calculation step (S3 in FIG. 1) for calculating the reaction temperature required to satisfy the information on the feedstock oil, information on the product oil, and the operating conditions based on the deterioration degree of the catalyst. Each step will be described below. Each step shown below is executed, for example, by the reaction temperature calculation device 1 of this embodiment. For example, S1 is executed by the acquisition unit 11, and S2 and S3 are executed by the calculation unit 13 in the computer main body 12.

[0014] <Information Acquisition Steps> The information acquisition step of this embodiment is a step of acquiring information on the feedstock oil, information on the product oil, and information on the operating conditions when a predetermined time has elapsed since the start of the reaction. The predetermined time after the start of the reaction is, for example, any t days after the start of the reaction. t may be an integer or a decimal, and for example, when t is 0.5, it means that 12 hours have elapsed since the start of the reaction. In addition, the time when t days have elapsed may be in the past, the present, or the future from the time when the information processing method of this embodiment is implemented. For example, when 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) is estimated.

[0015] (Information about raw material oil) An example of the information on the feedstock oil is information on the composition of the feedstock oil. An example of the information on the composition of the feedstock oil is information on the sulfur concentration in the feedstock oil.

[0016] Information on the sulfur concentration in the feedstock oil can be obtained by a method for measuring sulfur concentration known in the art, for example, ultraviolet fluorescence method, wavelength dispersive X-ray fluorescence method, etc. In addition, the sulfur concentration in the feedstock oil can be controlled by changing the feedstock oil. The information on the sulfur concentration in the feedstock oil is preferably a set value. That is, the sulfur concentration of the feedstock oil to be used can be used.

[0017] (Information on produced oil) An example of the information on the produced oil is information on the composition of the produced oil. An example of the information on the composition of the produced oil is information on the sulfur concentration in the produced oil.

[0018] Information on the sulfur concentration in the product oil can be obtained in the same manner as in the case of the feed oil described above. In this embodiment, the information on the sulfur concentration in the product oil is preferably a set value. That is, the sulfur concentration of the target product oil can be used.

[0019] (Information about operating conditions) Examples of information on operating conditions include information on hydrogen partial pressure, information on catalyst loading, feed rate, and information on hydrogen supply rate. For example, information on operating conditions is at least one of information on hydrogen partial pressure, information on catalyst loading, information on feed rate, and information on hydrogen supply rate. In particular, information on operating conditions preferably includes information on hydrogen partial pressure, information on catalyst loading, and information on feed rate, and more preferably includes all of information on hydrogen partial pressure, information on catalyst loading, information on feed rate, and information on hydrogen supply rate. In addition, operating conditions also include time information, such as an arbitrary t days after the start of the reaction.

[0020] The information on hydrogen partial pressure, catalyst loading amount, feedstock feed rate, and hydrogen feed rate can be determined by methods known in the art. The information on hydrogen partial pressure, catalyst loading amount, feedstock feed rate, and hydrogen feed rate can be controlled in the hydrotreating reaction of feedstock including atmospheric kerosene. The information on operating conditions is preferably a set value. That is, the planned operating conditions are used.

[0021] <Deterioration degree calculation step> The deterioration level calculation step in this embodiment is a step of calculating the deterioration level of the catalyst by a deterioration function based on the acquired information on the feed oil, information on the refined oil, and information on the operating conditions.

[0022] <Deterioration level> The degree of deterioration is expressed by the following formula 1. Φ=k t / k 0 formula 1 In the above formula 1, k 0 is the reaction rate constant of the catalyst at 0 days after the reaction (i.e., at the start of the reaction), and k t is the reaction rate constant of the catalyst after t days of any reaction. 0 , k t is the temperature T SOR is the reaction rate constant at

[0023] In this embodiment, the deterioration level of the catalyst can be calculated using a deterioration function based on the acquired information on the feed oil, the information on the product oil, and the information on the operating conditions.

[0024] <Degradation function> The deterioration function is a function for calculating the deterioration degree of the catalyst. In the present embodiment, the deterioration function is preferably a coke deterioration function related to the deterioration of the catalyst due to the deposition of coke. The coke deterioration function is not particularly limited as long as it is a function capable of calculating the deterioration degree related to the coke deterioration of the catalyst, and an example of the coke deterioration function is the deterioration function 1 represented by the following formula 2.

[0025] Φ=exp(-Dt) Equation 2 In the above formula 2, D is the deterioration coefficient of the active species of the catalyst, and t is the number of days elapsed since the reaction (days).

[0026] D can be calculated by the following formula 3. The following formula 3 is an equation that can calculate the deterioration coefficient of the active species of the catalyst using specific parameters, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

[0027]

number

[0028] In this specification, the term "required temperature" means a reaction temperature required to achieve a predetermined reaction condition. That is, the required temperature on day 0 is the temperature at the start of the reaction that is equal to or lower than the above S F , S P , LHSV, and the reaction temperature required to achieve the reaction conditions of P.

[0029] In this specification, the term "reference hydrogen partial pressure" refers to a standard pressure under actual reaction conditions. It is calculated as the average value of reaction pressures used when determining the hydrogen partial pressure coefficient a described later.

[0030] In this specification, the "reference reaction temperature" refers to the T obtained under the standard operating conditions that may actually be used. SOR means the average value of

[0031] In the above formula 3, T SOR represents the initial activity of the catalyst, and α represents the deactivation rate of the catalyst. That is, T SOR The larger the value of α, the greater the catalyst deterioration, and this deterioration behavior is reflected in the value of D.

[0032] In the above formula 3, (1 / S P n-1 -1 / S F n-1 The term represented by LHSV is the desulfurization reaction rate constant, and as mentioned above, S P , S F When the LHSV is set as a set value and the operation is performed under certain conditions, it becomes a constant. In the above formula 3, (P B / P) a The term represented by exp[Ec / R(1 / T B -1 / T SOR )] is a term that indicates temperature dependency and is a constant.

[0033] In the above formula 3, 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 information acquisition step described above. Note that the LHSV can be calculated by dividing the feed oil supply amount (volume / h) by the catalyst loading amount (volume).

[0034] As mentioned above, S F , LHSV, and P are controllable parameters. P is the sulfur concentration of the target product oil. F , S PThe deactivation coefficient of the active species of the catalyst can be calculated under the reaction conditions of , LHSV, and P. The method for determining n, which is the reaction order of the hydrotreating reaction of the feedstock oil containing vacuum distillation kerosene, will be described later.

[0035] (How to obtain basic deterioration parameters) In the above formula 3, α, P B ,a,Ec,T B , T SOR is a constant. Hereinafter, these parameters are collectively referred to as "basic deterioration parameters". The basic deterioration parameters are parameters determined according to the catalyst used, and may be obtained while performing a reaction in an actual machine, or may be obtained in advance on a bench scale based on the actual machine operating conditions. In this embodiment, it is preferable to obtain the parameters in advance on a bench scale based on the actual machine operating conditions. The basic degradation parameter P B ,a,Ec,T B Here is an example of how to calculate P. The method of calculating P from the deterioration behavior of the catalyst (change in reaction rate constant) analyzed from data obtained from the above-mentioned actual reaction or bench-scale reaction under actual operation conditions is shown below. B ,a,Ec,T B (How to find α, T SOR Two examples of how to calculate α and T are shown below, but the present invention is not limited to these. The first example is a method of calculating α and T from the deterioration behavior of the catalyst (change in reaction rate constant) analyzed from data obtained from the above-mentioned reaction in the actual equipment or from a bench-scale reaction based on the operating conditions of the actual equipment. SOR The second example is a method to obtain α and T from the reaction temperature profile analyzed from the data obtained in the above-mentioned actual reaction or bench-scale reaction based on the actual operation conditions. SOR This is how to find 2).

[0036] (P B ,a,Ec,T B (How to calculate) The method of obtaining the basic deterioration parameters in this embodiment is based on the deterioration behavior of the catalyst analyzed from data obtained from the above-mentioned reaction in the actual machine or the reaction in a bench scale under the operating conditions of the actual machine. The deterioration behavior (degree of deterioration) of this catalyst can be expressed by the following formula 4, which is based on the same concept as the above formula 1. Φ'=k t ' / k 0 ' expression 4 In the above formula 4, k 0 ' is the reaction rate constant of the catalyst at 0 days after the reaction (i.e., at the start of the reaction), and k t ' is the reaction rate constant of the catalyst after t days of any reaction. Note that k 0 ',k t ' is the temperature T SOR ' is the reaction rate constant at

[0037] The above-mentioned formula 4 is a deterioration function based on a reaction rate constant, similar to the above-mentioned formula 1. The reaction rate constant is expressed by the Arrhenius formula of the following formula 5.

[0038]

number

[0039] Temperature T at the start of reaction SOR Reaction rate constant k at 0 ' is k after t days of reaction t The reaction rate constant k 0 To obtain an activity equivalent to T t If it is assumed that Eq. (6) must be satisfied, then Eq. (4) and Eq. (5) give the following Eq. (6). Note that since the reaction in this embodiment is a hydrotreating reaction of a feed oil containing atmospheric distillation kerosene, the activation energy E is set to the desulfurization activation energy Ea (kJ / mol).

[0040]

number

[0041] (Ec and T B (How to calculate) The LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, and sulfur concentration in the feed oil are all constant, and the sulfur concentration in the produced oil is set to a constant value S Pn The reaction is carried out for a certain period of time so that the sulfur concentration in the resulting oil becomes S Pn In order to achieve this, the reaction temperature is increased while the reaction is being run. If the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis, and a regression line is drawn, y=a n x+b n (0 n ) is obtained. n and b n is a value that reflects the deterioration behavior of the catalyst. n is T in the above formula 6 SOR In the above formula 6, T SOR ' to b n Substituting, T t By substituting the actual reaction temperature into ', the deterioration degree Φ' after any reaction time of t days can be obtained. The activation energy Ea of desulfurization can be determined by the method described below. By plotting the logarithm of Φ' on the vertical axis against the reaction time on the horizontal axis and drawing a regression line, y=-a n ’ x(|-a n ’ |=a n ’ ) is obtained. n ’ represents the catalyst deterioration rate.

[0042] n types of sulfur concentration S Pn The same reaction was carried out for n a n , b n Then, in the same way as above, n ’ ​where n is an integer of 3 or more. The larger the value of n, the more accurate Ec can be obtained. On the other hand, if the value 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's obtained in this way n ’ and b n are substituted into the following formula 7. The following formula 7 is an equation that can calculate the activation energy and reference reaction temperature of coke, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

[0043] ln(a n ’ )=ln(A)-(Ec / Rb n ) Equation 7 In the above formula 7, 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)).

[0044] n a n ’ and b n For the combination of ln(a n ’ ) on the vertical axis, and 1 / b n Plot on the horizontal axis, draw a regression line, and determine its slope. Since this slope is Ec / R, the activation energy Ec of coke deterioration can be calculated by subtracting R from the slope.

[0045] Also, n b n By averaging T B can be sought.

[0046] Ec and T B In determining the above, it is preferable that the LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, and sulfur concentration in the feed oil are set to conditions that correspond to the actual operating conditions of the plant. Such LHSV is, for example, 1 to 10 h -1The hydrogen partial pressure is, for example, 3 to 7 MPa, and the hydrogen / feedstock ratio is, for example, 50 to 400 [Nm 3 / kL], and the sulfur concentration in the feed oil is, for example, 0.05 to 0.8 mass %. n types of sulfur concentration S Pn Similarly, it is preferable to set the conditions for S according to the actual operating conditions. Pn is, for example, 0.001 mass % or less. The reaction period is, for example, 100 to 1500 days.

[0047] (P B and how to find a) With the LHSV, hydrogen / feed oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the produced oil as constant conditions, the hydrogen partial pressure P m The reaction is carried out for a certain period of time under the above conditions. Because the catalyst deteriorates during the reaction, the reaction temperature is increased in order to keep the sulfur concentration in the resulting oil at a certain value. If the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis, a regression line is drawn, y=a m x+b m (0 m ) is obtained. On this line, b m is T in the above formula 6 SOR In the above formula 6, T SOR ' to b m Substituting, T t By substituting the actual reaction temperature into ', the degree of deterioration Φ' after any reaction time of t days is obtained. By plotting the logarithm of Φ' on the vertical axis against the reaction time on the horizontal axis and drawing a regression line, y=-a m ’ x(|-a m ’ |=a m ’ ) is obtained. m ’ represents the catalyst deterioration rate.

[0048] m types of hydrogen partial pressure P m The same reaction was carried out for m a m , b m Then, in the same way as above, m a​m ’ where m is an integer of 3 or more. The larger the value of m, the more accurate a can be obtained. On the other hand, if the value 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's obtained in this way m ' and P m are substituted into the following formula 8. The following formula 8 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.

[0049] ln(a m ’ )=-aln(P m )+B1 formula 8 In the above formula 8, B1 can be 0.

[0050] m a m ' and P m For the combination of ln(a m ’ ) on the vertical axis, and ln(P m ) on the horizontal axis, draw a regression line, and determine its slope. This slope is the hydrogen partial pressure coefficient a.

[0051] In addition, the hydrogen partial pressure P m By averaging P B can be sought.

[0052] a and P B In determining the above, it is preferable that the LHSV, hydrogen / feed oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil are set to conditions that correspond to the actual operating conditions of the plant. Such LHSV is, for example, 1 to 10 h -1 The hydrogen / feedstock ratio is, for example, 50 to 400 [Nm 3 / kL], the sulfur concentration in the feed oil is, for example, 0.05 to 0.8 mass %, and the sulfur concentration in the product oil is, for example, 0.001 mass % or less. m hydrogen partial pressure Pm Similarly, it is preferable to set the conditions for P to match the actual operating conditions. m The pressure is, for example, 3 to 7 MPa. The reaction period is, for example, 100 to 1500 days.

[0053] (α and T SOR How to calculate 1) In the 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, and sulfur concentration in the product oil are the assumed operating conditions of the actual plant. Since the catalyst deteriorates due to the reaction, the reaction temperature is raised while operating. The assumed operating conditions of the actual plant are (Ec and T B How to find P B The operating conditions explained in (a) and (b) are given as examples. If the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis, and a regression line is drawn, y=a α x+b α We obtain a line represented by the following equation. α is a value correlated to α in the above formula 3, and b α is T in the above formula 3 SOR In the above formula 6, T SOR ' to b α Substituting, T t By substituting the actual reaction temperature into ', the degree of deterioration Φ' after any reaction time of t days is obtained. By plotting the logarithm of Φ' on the vertical axis against the reaction time on the horizontal axis and drawing a regression line, y=-a α ’ x(|-a α ’ |=a α ’ We obtain a straight line represented by a α ’ represents the catalyst deterioration rate.

[0054] Operating condition S P , S F , LHSV, P, and P obtained by the above method B ,a,Ec,T B、 T SOR (i.e., b α) into the above formula 3 to find D. Substituting the found D into the above formula 2 gives Φ. In this case, 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 by changing α so that α is 0<α, then y=-α α ” x(|-a α ” |=a α ” For each value of α, multiple straight lines represented by α ” And the above a α ’ can be set as α in the above formula 3 when these values ​​are equal.

[0055] (α and T SOR How to find 2) (α and T SOR Method 1) Carry out the same reaction as above, and find y=a α x+b α Obtain a straight line represented by b α T in the above formula 3 SOR The operating condition is S P , S F , LHSV, P, and P obtained by the above method B ,a,Ec,T B、 T SOR (i.e., b α ) into the above formula 3 to obtain D. Substituting the obtained D into the above formula 2, Φ is obtained. In this case, Φ is a function of α. Substituting the obtained Φ into Φ' in the above formula 6, T SOR (i.e., b α ) in the above formula 6 SOR ’ Substituting for T t To summarize, T t ' is a function of α. The measured reaction temperature T obs T for t ' ratio (T t ' / T obs ) is 1, the α in the above formula 3 can be used. Similarly, N reaction temperatures T obs T for t ' ratio (T t ' / Tobs ) and the value of α at which their average approaches 1 is preferably used as α in the above formula 3. N is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

[0056] (Modification of degradation function) Modifications of the point spread function will be described below. Point spread function 1-1 expressed by the following formula 9 may be used as the point spread function.

[0057] Φ=exp(-D't) Equation 9 In the above formula 9, D' is the deterioration coefficient of the active species of the catalyst, and t is the number of days elapsed since the reaction (days).

[0058] D' can be calculated using the following formula 10.

[0059]

number

[0060] In the above formula 10, S F , S P , LHSV, and P are the same as those in the above formula 3. In the above formula 10, G is a value substituted based on the information on the feed oil and the information on the operating conditions acquired in the above-mentioned information acquisition step. Specifically, G is the amount of hydrogen supplied (Nm 3 It can be calculated by dividing the feed rate of the raw oil (kL / hour) by the feed rate of the raw oil (kL / hour).

[0061] In this specification, the "reference hydrogen / feed oil ratio" refers to a standard hydrogen / feed oil ratio under actual reaction conditions. It is calculated as the average value of the hydrogen / feed oil ratio used to determine the hydrogen / feed oil ratio coefficient b described later.

[0062] In the formula 10, (G B / G) b The term represented by is a term that indicates the hydrogen / feed oil ratio dependency, and as described above, when G is set as a set value and operation is performed under constant conditions, it becomes a constant.

[0063] P B ,a,Ec,T B , T SOR can be calculated in the same manner as described above for Equation 3. B We will explain how to calculate b and α'.

[0064] G B , b is P B ,a,Ec,T B , T SOR Similarly, G is a parameter determined according to the catalyst used, and may be determined while carrying out 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 G in advance on a bench scale based on the operating conditions of the actual machine. B We will explain how to calculate b.

[0065] (G B , how to find b) The method of determining the basic deterioration parameters in this embodiment is based on the deterioration behavior of the catalyst analyzed from data obtained in the above-mentioned reaction in the actual machine or in a bench-scale reaction based on the operating conditions of the actual machine.

[0066] The LHSV, hydrogen partial pressure, sulfur concentration in the feed oil, and sulfur concentration in the produced oil are constant, and the hydrogen / feed oil ratio G h The reaction is carried out for a certain period of time under the above conditions. Because the catalyst deteriorates during the reaction, the reaction temperature is increased in order to keep the sulfur concentration in the resulting oil at a certain value. If the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis, a regression line is drawn, y=a h x+b h (0 h ) is obtained. On this line, b h is T in the above formula 6 SOR In the above formula 6, T SOR ' to b h Substituting, T t ’ By substituting the actual reaction temperature into the above, the degree of deterioration Φ' after any reaction time t days has elapsed can be obtained. By plotting the logarithm of Φ' on the vertical axis against the reaction time on the horizontal axis and drawing a regression line, y=-a h ’ x(|-a h ’ |=a h ’ ) is obtained. h ’ represents the catalyst deterioration rate.

[0067] h types of hydrogen / feed oil ratio G h The same reaction was carried out for h a h , b h Then, using the same method as above, find h a h ’ Here, h is an integer of 3 or more. The larger the value of h, the more accurate b can be obtained. On the other hand, if the value 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 obtained in this way h ' and G h are substituted into the following formula 11. The following formula 11 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 unit, etc.

[0068] ln(a h ')=-bln(G h )+B3 Equation 11 In the above formula 11, B3 can be 0.

[0069] h a h ' and G h For the combination of ln(a h ') on the vertical axis, and ln(G h ) on the horizontal axis, draw a regression line, and determine the slope. This slope is the hydrogen / feed oil ratio coefficient b.

[0070] In addition, the above h types of hydrogen / feedstock ratio G h By averaging, G B can be sought.

[0071] b and G B In determining the above, it is preferable that the LHSV, hydrogen partial pressure, sulfur concentration in the feed oil, and sulfur concentration in the product oil are set to conditions conforming to the operating conditions of an actual plant. Such LHSV is, for example, 1 to 10 h -1 The hydrogen partial pressure is, for example, 3 to 7 MPa, the sulfur concentration in the feed oil is, for example, 0.05 to 0.8 mass %, and the sulfur concentration in the product oil is, for example, 0.001 mass % or less. h types of hydrogen / feed oil ratio G h Similarly, it is preferable to set the conditions for G according to the actual operating conditions. h For example, 50 to 400 [Nm 3 / kL]. The reaction period is, for example, 100 to 1500 days.

[0072] In addition, for α', the method of calculating α (α and T SOR How to find 1) and (α and T SOR This can be calculated using the same method as 2).

[0073] <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 feed oil, the information on the product oil, and the operating conditions based on the deterioration degree of the catalyst. The reaction temperature is preferably calculated using a deterioration rate equation based on the Arrhenius equation.

[0074] <Deterioration rate formula> The deterioration rate equation is based on the Arrhenius equation represented by the above-mentioned equation 5. Similar to the calculation method of the above-mentioned equation 6, the following equation 12 is derived from the above-mentioned equations 1 and 5.

[0075]

number

[0076]

number

[0077] In the above formula 13, T obtained by the above method SOR By substituting Φ, T t (K) can be obtained. The activation energy of the desulfurization reaction in the above formula 13 can be calculated as follows.

[0078] (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 5. An example will be described below.

[0079] First, determine the reaction order of the desulfurization reaction of feedstock oil containing atmospheric distillation kerosene. The reaction temperature, hydrogen partial pressure, hydrogen / feedstock ratio, and sulfur concentration in the feedstock oil are all constant, and the reaction is carried out under the LHSV(x) condition, and the sulfur concentration in the resulting oil is measured. The S F The sulfur concentration in the feed oil is expressed as S P Substitute the sulfur concentration in the resulting oil obtained in for LHSV(x). Plot the result on the left side of the equation on the vertical axis and 1 / LHSV on the horizontal axis. In this case, the vertical axis is a function of n.

[0080]

number

[0081] A similar reaction is carried out for x types of LHSV(x), and x plots of the above are obtained. Based on the obtained plots, a regression line is drawn 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 ))), where x is 1 / LHSV and c is k. Calculate the correlation function using Excel or similar, and find n for which the correlation coefficient is closest to 1. The resulting n is the reaction order. Note that n should be calculated to the first decimal place.

[0082] The above x is an integer of 3 or more. 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 time to obtain n, which is not efficient. In this embodiment, x is preferably 3 to 20, and more preferably 3 to 10.

[0083] In determining n, it is preferable that the reaction temperature, hydrogen partial pressure, hydrogen / feedstock ratio, and sulfur concentration in the feedstock be conditions that correspond to the operating conditions of an actual plant. The reaction temperature is, for example, 280 to 350°C, the hydrogen partial pressure is 3 to 5 MPa, and the hydrogen / feedstock ratio is 50 to 400 [Nm 3 / kL], and the sulfur concentration in the feed oil is 0.05 to 0.8 mass %. Similarly, it is preferable that the x types of LHSV(x) are set to conditions that correspond to the actual operating conditions. -1 It is.

[0084] If the activation energy E in the Arrhenius equation expressed by the above formula 5 is taken as the activation energy Ea of desulfurization and the natural logarithm of both sides is taken, the following formula 15 is obtained.

number

[0085] The hydrogen partial pressure, hydrogen / feed oil ratio, LHSV, and sulfur concentration in the feed oil are constant, and the reaction is carried out at a reaction temperature of T(y), and the sulfur concentration in the product oil is measured. F The sulfur concentration in the feed oil is expressed as S P The sulfur concentration in the product oil obtained in is substituted for LHSV, and the above obtained n is substituted for LHSV to determine the reaction rate constant k. The obtained reaction rate constant is substituted into the above equation 15, and the result of the left side obtained (lnk) is plotted on the vertical axis and 1 / T (1 / T(y)) is plotted on the horizontal axis.

[0086] The same reaction is carried out for y different reaction temperatures T(y), and y plots as shown above are obtained. A regression line is drawn from the obtained plots, and its slope is calculated. Since this slope is Ea / R, the activation energy of desulfurization Ea can be calculated by subtracting R from the slope.

[0087] The above y is an integer of 3 or more. 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 time to obtain Ea, which is not efficient. In this embodiment, y is preferably 3 to 20, and more preferably 3 to 10.

[0088] In determining Ea, the hydrogen partial pressure, hydrogen / feed oil ratio, LHSV, and sulfur concentration in the feed oil are preferably set to conditions that correspond to the operating conditions of an actual plant. The hydrogen partial pressure is, for example, 3 to 5 MPa, and the hydrogen / feedstock ratio is 50 to 400 [Nm 3 / kL] and LHSV is 1-10h -1 The sulfur concentration in the feed oil is 0.05 to 0.8 mass %. Similarly, it is preferable that the reaction temperature T(y) of the y types is set to a condition conforming to the operating conditions of the actual equipment. Such T(y) is 280 to 350°C.

[0089] By substituting each parameter thus obtained into the above formula 13, the reaction temperature T required to achieve the desired reaction conditions can be calculated. t can be sought.

[0090] Actual reaction temperature T obs The reaction temperature T obtained by the information processing method of this embodiment t The ratio of T t / T obs is preferably 0.97 to 1.03, and more preferably 0.985 to 1.015, in °C. t / T obs When the reaction temperature is within the above range, it can be determined that the reaction temperature can be estimated with high accuracy.

[0091] <Information output step> The method may further include an information output step (S4 in FIG. 1) of outputting information indicating the reaction temperature thus obtained. For example, S4 is executed by the output unit 14.

[0092] <Hydrotreatment reaction of feedstock oil including atmospheric distillation kerosene> The hydrotreating reaction of feedstock oils including atmospheric distillation kerosene is outlined below. Atmospheric kerosene is a fraction obtained by atmospheric distillation of crude oil and has a boiling point range of 130 to 280° C. The density of atmospheric kerosene is 0.78 to 0.81 g / mL. The content of atmospheric kerosene in the feedstock oil may be, for example, 70% by volume or more. In addition, examples of oil types other than atmospheric distillation kerosene contained in the feed oil include naphtha.

[0093] The hydrotreating reaction of the feedstock containing atmospheric distillation kerosene can be carried out by contacting the feedstock containing atmospheric distillation kerosene with a hydrotreating catalyst in the presence of hydrogen. The hydrotreating catalyst is not particularly limited, and hydrotreating catalysts known in the art can be used. Various catalyst supports can be used, such as 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 ones include alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia, and particularly preferred ones include alumina, and among aluminas, γ-alumina is particularly preferred. These inorganic oxides may be used alone or in combination of two or more.

[0094] The metal contained in the carrier as an active component is at least one metal selected from metals in Group 6 and Groups 8 to 10 of the periodic table, and is preferably molybdenum, tungsten, cobalt, and nickel. These metals are effective in any form of metal, metal oxide, or metal sulfide, and may be present in a form in which the metal is bonded to the catalyst carrier by ion exchange or the like. The content of this metal component is usually within the range of about 10 to 25 mass% based on the catalyst and calculated as an oxide. If the metal content is less than 10 mass%, the absolute amount of the metal acting as an active site is small, so that hydrotreating activity such as desulfurization activity (hereinafter simply referred to as hydrotreating activity) is not expressed, and conversely, if the content of the supported metal is too much than 25 mass%, the metal aggregates and the number of active sites decreases, resulting in a decrease in hydrotreating activity. Furthermore, if necessary, phosphorus, boron, zinc, zirconia, etc. can be contained in addition to the active metals consisting of metals in Groups 6 and 8 of the periodic table. In applying the method of the present invention, there is no restriction on the form of the catalyst bed, and the method can be applied to reactors having catalyst beds of, for example, fixed beds, moving beds, fluidized beds, etc.

[0095] The conditions for the hydrotreating reaction of the feedstock oil containing atmospheric distillation kerosene are generally as follows: reaction temperature is 280 to 350°C, hydrogen partial pressure is 3 to 7 MPa, preferably 4 to 5 MPa, LHSV is 1 to 10 hr. -1 , preferably 2 to 8 hours -1 The hydrogen / feed oil ratio is 50-400 (Nm 3 / kL), preferably 100 to 300 (Nm 3 / kL).

[0096] The sulfur concentration in the feedstock oil containing atmospheric distilled kerosene is usually 0.05 to 0.8% by mass, and the sulfur concentration in the product oil is usually 0.001% by mass or less.

[0097] <Reaction temperature calculation device> The reaction temperature calculation device of this embodiment includes an acquisition unit that acquires information regarding the feedstock oil, information regarding the product oil, and information regarding operating conditions after a predetermined time has elapsed since the start of the reaction, regarding the hydrotreating reaction of the feedstock oil including atmospheric distilled kerosene, and a calculation unit that calculates a degree of catalyst deterioration using a deterioration function based on the information regarding the feedstock oil, information regarding the product oil, and information regarding the operating conditions acquired by the acquisition unit, and calculates the reaction temperature required to satisfy the information regarding the feedstock oil, information regarding the product oil, and the operating conditions based on the calculated degree of catalyst deterioration.

[0098] The reaction temperature calculation device 1 of this embodiment is configured using an information processing device such as a personal computer, a server device, or a dedicated device. The reaction temperature calculation device 1 may be configured using one or more information processing devices. For example, the reaction temperature calculation device 1 may be constructed as a cluster machine, may be constructed as a cloud, or may be constructed in any manner. Specifically, the reaction temperature calculation device 1 has an acquisition unit 11 and a computer main body 12 that processes information from the acquisition unit, as shown in FIG. 4. The reaction temperature calculation device 1 may have an output unit 14 that outputs information processed in the computer main body 12 to the outside. These components are realized, for example, by a hardware processor such as a CPU (Central Processing Unit) executing a program (software). In addition, some or all of these components may be realized by hardware (including circuitry) such as an LSI (Large Scale Integrated circuit), an ASIC (Application Specific Integrated Circuit), an FPGA (Field-Programmable Gate Array), or a GPU (Graphics Processing Unit), or may be realized by cooperation between software and hardware. The program may be stored in advance in a storage device (a storage device with a non-transient storage medium) such as a hard disk drive (HDD) or flash memory, or may be stored in a removable storage medium (non-transient storage medium) such as a DVD or CD-ROM, and installed in the storage device by mounting the storage medium in a drive device. The storage device may be configured, for example, with a HDD, flash memory, an electrically erasable programmable read only memory (EEPROM), a read only memory (ROM), or a random access memory (RAM).

[0099] The acquisition unit 11 receives predetermined information input by a reaction operator and transmits the information acquired by this input to the computer body 12. The information acquired by the acquisition unit 11 in this embodiment is information on the feedstock oil when a predetermined time has elapsed since the start of the reaction, information on the product oil, and information on the operating conditions, regarding the hydrotreating reaction of the feedstock oil including atmospheric distillation kerosene. The information on the feedstock oil when a predetermined time has elapsed since 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 above-mentioned information acquisition step. The acquisition unit 11 only needs to acquire information on the feedstock oil when a predetermined time has elapsed since the start of the reaction, information on the product oil, and information on the operating conditions, and the acquisition method is not particularly limited.

[0100] 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 be a touch panel or the like. Note that acquisition units for acquiring various information may be configured separately and each may be independently connected to the computer main body 12. Also, the acquisition unit 11 may be configured to directly acquire each of the above-mentioned information from a computer or the like used for controlling the reactor, etc., via a wired or wireless connection.

[0101] The computer body 12 is, for example, a so-called computer capable of processing various information. The computer body 12 includes a calculation unit 13. For example, a predetermined program is incorporated in the computer body 12, and the calculation unit 13 is functionally configured by executing this program. Specifically, in the calculation unit 13, based on the information on the raw oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit 11 at the time when a predetermined time has elapsed since the start of the reaction, the deterioration degree of the catalyst is calculated by a deterioration function, and based on the deterioration degree of the catalyst, the information on the raw oil, the information on the product oil, and the reaction temperature required to satisfy the operating conditions are calculated. The deterioration function is as described above. As described above, the reaction temperature can be obtained, for example, from the deterioration rate formula. For example, the calculation unit 13 executes the deterioration degree calculation step and the reaction temperature calculation step 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 a non-volatile or volatile semiconductor memory (for example, a RAM (Random Access Memory), a ROM (Read Only Memory), a flash memory, an EPROM (Erasable Programmable Read Only Memory), or an EEPROM (Electrically Erasable Programmable Read Only Memory)). For example, the calculation unit 13 may be a microcontroller such as an MCU.

[0102] The calculation unit 13 may output to the output unit 14 information regarding the feed oil obtained as described above, information regarding the refined oil, and information indicating the reaction temperature required to satisfy the operating conditions.

[0103] 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. The output unit 14 in this embodiment is configured by a display unit such as a CRT display, a liquid crystal display, or a PDP, but is not limited to this and may be configured to output to a printing unit such as a printer, or other devices (for example, a computer used to control the hydrotreating reaction of feedstock oil including atmospheric distilled kerosene), etc. The output unit 14 may also be a combination of these. For example, the output unit 14 executes the information output step described above.

[0104] In addition, in this embodiment, a reaction temperature calculation program for causing a computer to function as a reaction temperature calculation device and a non-transitory computer readable recording medium storing the program are provided. Examples of the non-transitory computer readable recording medium include magnetic tape (digital data storage (DSS) and the like), magnetic disk (hard disk drive (HDD), flexible disk (FD), and the like), optical disk (compact disk (CD), digital versatile disk (DVD), Blu-ray disk (BD), and the like), magneto-optical disk (MO), and flash memory (solid state drive (SSD), memory card, USB memory, and the like).

[0105] <Method of using the information processing method and reaction temperature calculation device> According to the information processing method and the reaction temperature calculation device of this embodiment, it is possible to estimate the reaction temperature required to achieve a predetermined reaction condition for the hydrotreating reaction of the feedstock oil including atmospheric distillation kerosene. According to the information processing method and the reaction temperature calculation device of this embodiment, it is possible to obtain a plot of the estimated value of the reaction temperature over time. Based on the relationship between the plot and the maximum temperature of the equipment use, the following applications are possible.

[0106] The first application method is to estimate the operation time (number of days) required to replace the catalyst under a given reaction condition. That is, the plot can estimate the time at which the temperature reaches the maximum temperature for use with the equipment, and the operation time (number of days) required to replace the catalyst can be estimated from the time. In addition, if the estimated reaction temperature is not equal to or lower than the equipment set temperature, an information processing method shown in S4-1 to 4-3 of FIG. 2 may be performed. The information processing method shown in S4-1 to 4-3 of FIG. 2 includes an information acquisition step (S4-1 of FIG. 2) for acquiring information on the target reaction temperature, a deterioration degree calculation step (S4-2 of FIG. 2) for calculating the deterioration degree of the catalyst by a deterioration function based on the acquired target reaction temperature, and a reaction condition calculation step (S4-3 of FIG. 2) for calculating information on the feed oil, information on the product oil, and information on the operating conditions required to satisfy the target reaction temperature based on the deterioration degree. The method may further include an information output step (S4-4 of FIG. 2) for outputting the information on the feed oil, information on the product oil, and information on the operating conditions obtained in this manner. Specifically, for example, when the degradation function 1 expressed by the above-mentioned formula 2 is used, T t Substitute the desired reaction temperature into and calculate Φ. Substitute the obtained Φ into the above formula 2 to calculate D. Substitute the obtained D into the above formula 3 to calculate S so that the equation of the above formula 3 holds. P , S F , LHSV, and P. In the above combination, for example, S P , S F may be used as a set value to obtain P and LHSV. As the degradation function, either degradation function 1 or degradation function 1-1 expressed by the above formula 2 may be used. Each of the above steps is executed, for example, by the reaction temperature calculation device 1 of this embodiment. For example, S4-1 is executed by the acquisition unit 11, S4-2 and S4-3 are executed by the calculation unit 13 in the computer main body 12, and S4-4 is executed by the output unit 14. The target temperature may be stored in advance in the calculation unit 13 in the computer main body 12.

[0107] The second application method is to estimate the reaction conditions (throughput (LHSV) and the like) for achieving a predetermined operation time. Such an information processing method is represented by S1A to 3A in FIG. 3. The information processing method represented by S1A to 3A in FIG. 3 includes an information acquisition step (S1A in FIG. 3) for acquiring information on a target reaction temperature at a predetermined operation time, a deterioration degree calculation step (S2A in FIG. 3) for calculating a deterioration degree of the catalyst by a deterioration function based on the acquired target reaction temperature, and a reaction condition calculation step (S3A in FIG. 3) for calculating information on the feed oil, information on the product oil, and information on the operation conditions required to satisfy the target reaction temperature based on the deterioration degree. The method may further include an information output step (S4A in FIG. 3) for outputting the information on the feed oil, information on the product oil, and information on the operation conditions obtained in this manner. Specifically, for example, when the deterioration function 1 represented by the above-mentioned formula 2 is used, T t The desired reaction temperature after a certain operation time of t days is substituted into the above equation to obtain Φ. The obtained Φ is substituted into the above equation 2 to obtain D. The obtained D is substituted into the above equation 3 to obtain S such that the equality of the above equation 3 is satisfied. P , S F , LHSV, and P. In the above combination, for example, S P , S F may be used as a set value to obtain P and LHSV. As the degradation function, either degradation function 1 or degradation function 1-1 expressed by the above formula 2 may be used. Each of the above steps is executed, for example, by the reaction temperature calculation device 1 of this embodiment. For example, S1A is executed by the acquisition unit 11, S2A and S3A are executed by the calculation unit 13 in the computer main body 12, and S4A is executed by the output unit 14. The target temperature for a predetermined operation time may be stored in advance in the calculation unit 13 in the computer main body 12. EXAMPLES

[0108] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0109] [Example] A hydrotreating reaction was carried out on a bench scale by contacting a feedstock oil containing 80% by volume of atmospheric distilled kerosene with a hydrotreating catalyst. Based on the obtained results, the degradation function was calculated. The basic degradation parameters in the above-mentioned formula 3 were calculated by the above-mentioned method, and were α = 0.00005, P B =3.234(MPa), a=2, Ec=83.1(kJ / mol), T B =625(K), T SOR =578.1(K), n=1.3. The reaction was carried out in an actual reactor using the same feedstock and hydrotreating catalyst as in the bench-scale hydrotreating reaction. F =0.18(mass%), P=4.48(MPa), LHSV=4.49(h -1 ), S P = 0.0006 (mass%). In addition, the activation energy of desulfurization was calculated in advance using the method described above and was found to be Ea = 120 (kJ / mol). These basic deterioration parameters and reaction conditions were substituted into the above formula 3 to obtain D. The obtained D and the reaction time t were substituted into the above formula 2 to obtain Φ. The obtained Φ, Ea, and T SOR Substituting into the above formula 13, the required temperature T after any reaction t days has elapsed t Table 1 shows the actual reaction temperatures at t = 245 days, 505 days, and 1141 days, as well as the required temperatures T t , and the required temperature T t / The ratio of the actual reaction temperature is shown.

[0110] [Table 1]

[0111] As shown in Table 1, the required temperature T t It was found that the reaction temperature was almost the same as the measured reaction temperature. [Explanation of symbols]

[0112] 1. Reaction temperature calculation device 11...Acquisition part 12...Calculator body 13... Arithmetic section 14 Output section

Claims

1. With respect to the hydrotreating reaction of the feedstock oil including atmospheric distillation kerosene, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on the operating conditions at a predetermined time after the start of the reaction; a deterioration degree calculation step of calculating a deterioration degree of a catalyst by a deterioration function based on the acquired information on the feed 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 required to satisfy the operating conditions based on the deterioration degree of the catalyst, The information on the feedstock oil is information on the sulfur concentration in the feedstock oil, the information on the product oil is information on the sulfur concentration in the product oil, and the information on the operating conditions is information on the hydrogen partial pressure, information on the catalyst loading amount, and information on the feedstock oil supply amount, The information processing method, wherein the degradation function is a function expressed by the following formula 2: Φ=exp(-Dt) Formula 2 In the above formula 2, Φ is the degree of deterioration of the catalyst, D is the deterioration coefficient of the active species of the catalyst and is calculated using the following formula 3, and t is the number of days elapsed since the reaction began (days). [0010] In the above formula 3, α is a catalyst constant (a constant representing the deterioration rate of the catalyst), S F is the sulfur concentration (mass%) in the feedstock oil after t days of any reaction, S P is the sulfur concentration (mass%) in the product oil after t days of any reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation kerosene, LHSV is the liquid hourly space velocity (h -1 ) after t days of any reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any 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 according to the catalyst used. The constants are determined while carrying out the reaction in an actual reaction vessel, or are determined in advance on a bench scale based on the operating conditions of the actual reaction vessel.

2. Regarding a hydrotreating reaction of a feedstock oil including atmospheric distillation kerosene, 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 catalyst by a deterioration function based on the acquired information on the feed 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 required to satisfy the operating conditions based on the deterioration degree of the catalyst, The information on the feedstock oil is information on the sulfur concentration in the feedstock oil, the information on the product oil is information on the sulfur concentration in the product oil, and the information on the operating conditions is information on the hydrogen partial pressure, information on the catalyst loading amount, and information on the feedstock oil supply amount, The information processing method, wherein the degradation function is a function expressed by the following formula 9. Φ=exp(-D't) Equation 9 In the above formula 9, Φ is the degree of deterioration of the catalyst, D′ is the deterioration coefficient of the active species of the catalyst and is calculated using the following formula 10, and t is the number of days elapsed since the reaction began (days). [0025] In the above formula 10, α' is a catalyst constant (a constant representing the deterioration rate of the catalyst), S F is the sulfur concentration (mass%) in the feed oil after t days of any reaction, S P is the sulfur concentration (mass%) in the product oil after t days of any reaction, n is the reaction order of the hydrotreating reaction of the feed oil containing atmospheric distilled kerosene, LHSV is the liquid hourly space velocity (h -1 ) after t days of any reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any reaction, a is the hydrogen partial pressure coefficient, G B is the reference hydrogen / feed oil ratio (Nm 3 / kL), 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). α', P B , a, G B , b, Ec, T B , and T SOR are constants determined depending on the catalyst used. The constants are determined while performing the reaction in an actual machine, or are determined in advance on a bench scale based on the operating conditions of the actual machine.

3. A reaction temperature calculation device comprising: an acquisition unit that acquires information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of a hydrotreatment reaction of a feedstock oil including atmospheric distillation kerosene; and a calculation unit that calculates a catalyst deterioration level using a deterioration 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, and calculates a reaction temperature required to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions based on the calculated deterioration level of the catalyst, The information on the feedstock oil is information on the sulfur concentration in the feedstock oil, the information on the product oil is information on the sulfur concentration in the product oil, and the information on the operating conditions is information on the hydrogen partial pressure, information on the catalyst loading amount, and information on the feedstock oil supply amount, The reaction temperature calculation device, wherein the degradation function is a function expressed by the following equation 2. Φ=exp(-Dt) Formula 2 In the above formula 2, Φ is the degree of deterioration of the catalyst, D is the deterioration coefficient of the active species of the catalyst and is calculated using the following formula 3, and t is the number of days elapsed since the reaction began (days). [0030] In the above formula 3, α is a catalyst constant (a constant representing the deterioration rate of the catalyst), S F is the sulfur concentration (mass%) in the feedstock oil after t days of any reaction, S P is the sulfur concentration (mass%) in the product oil after t days of any reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation kerosene, LHSV is the liquid hourly space velocity (h -1 ) after t days of any reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any 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 according to the catalyst used. The constants are determined while carrying out the reaction in an actual reaction vessel, or are determined in advance on a bench scale based on the operating conditions of the actual reaction vessel.

4. A reaction temperature calculation device comprising: an acquisition unit that acquires 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, regarding a hydrotreating reaction of a feedstock oil including atmospheric distilled kerosene; and a calculation unit that calculates a degree of catalyst deterioration using a deterioration function based on the information on the feedstock oil, information on the product oil, and information on the operating conditions acquired by the acquisition unit, and calculates a reaction temperature required to satisfy the information on the feedstock oil, information on the product oil, and the operating conditions based on the calculated degree of catalyst deterioration, The information on the feedstock oil is information on the sulfur concentration in the feedstock oil, the information on the product oil is information on the sulfur concentration in the product oil, and the information on the operating conditions is information on the hydrogen partial pressure, information on the catalyst loading amount, and information on the feedstock oil supply amount, The reaction temperature calculation device, wherein the degradation function is a function expressed by the following equation 9. Φ=exp(-D't) Equation 9 In the above formula 9, Φ is the degree of deterioration of the catalyst, D′ is the deterioration coefficient of the active species of the catalyst and is calculated using the following formula 10, and t is the number of days elapsed since the reaction began (days). [0045] In the above formula 10, α' is a catalyst constant (a constant representing the deterioration rate of the catalyst), S F is the sulfur concentration (mass%) in the feed oil after t days of any reaction, S P is the sulfur concentration (mass%) in the product oil after t days of any reaction, n is the reaction order of the hydrotreating reaction of the feed oil containing atmospheric distilled kerosene, LHSV is the liquid hourly space velocity (h -1 ) after t days of any reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any reaction, a is the hydrogen partial pressure coefficient, G B is the reference hydrogen / feed oil ratio (Nm 3 / kL), 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). α', P B , a, G B , b, Ec, T B , and T SOR are constants determined depending on the catalyst used. The constants are determined while performing the reaction in an actual machine, or are determined in advance on a bench scale based on the operating conditions of the actual machine.

5. A reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device according to claim 3 or 4.

6. A non-transitory computer readable recording medium storing the program according to claim 5.

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