Information processing method, silicon concentration calculation device, silicon concentration calculation program, and non-temporarily readable recording medium for computers.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- COSMO OIL CO LTD
- Filing Date
- 2022-09-30
- Publication Date
- 2026-08-03
AI Technical Summary
【0010】 本発明によれば、触媒を充填した固定床流通式反応器にケイ素化合物を含むコーカー分解ナフサを含む原料油及び水素を流通させて行う水素化処理反応に関して、反応を開始してから所定時間経過した際の反応器出口から排出される生成油中のケイ素濃度を推定することができる情報処理方法、及び前記ケイ素濃度を推定することができるケイ素濃度算出装置、コンピュータを、前記ケイ素濃度算出装置として機能させるためのケイ素濃度算出プログラム、及び前記プログラムを記憶したコンピュータの非一時的可読記録媒体を提供することができる。
Smart Images
Figure 0007899031000019 
Figure 0007899031000020 
Figure 0007899031000021
Abstract
Description
[Technical Field]
[0001] The present invention relates to an information processing method, a silicon concentration calculation device, a silicon concentration calculation program, and a non-temporarily readable recording medium for a computer. [Background technology]
[0002] Due to the decline in demand for heavy oil, there is a need for technologies that can efficiently convert atmospheric distillation residue oil, which is the main base material for heavy oil and is obtained by processing crude oil with an atmospheric distillation unit, and vacuum distillation residue oil, which is obtained by processing the atmospheric distillation residue oil with a vacuum distillation unit, into light oil with high added value.
[0003] As a technology for converting heavy oil base to light oil, a process is known that utilizes a fraction obtained by hydrothermating (hydrodesulfurizing) the coker cracked fraction, which is obtained by thermally cracking the coker cracked fraction in a heavy oil thermal cracking unit (hereinafter also referred to as a "coker unit"). Of the coker cracked fraction, the light fraction (coker cracked naphtha) is treated in a catalytic reforming reactor after hydrothermation to produce a fraction containing high value-added basic chemicals. The heavy fraction (heavy coker cracked hydrocarbon oil) is treated in a fluid catalytic cracking unit after hydrothermation to produce intermediate fractions such as gasoline, kerosene, and diesel fuel.
[0004] Incidentally, in coker units, silicon-based defoaming agents are used to suppress foaming in the reaction drum. As a result, silicon compounds derived from the defoaming agent are mixed into the fraction obtained by thermal decomposition in the coker unit. These silicon compounds are known to be poisonous substances for the hydrogenation catalyst used in the hydrogenation process. Furthermore, these silicon compounds are also known to be permanent poisonous substances for the catalytic reforming catalyst packed into the catalytic reforming reactor. Therefore, it is necessary to ensure that the hydrogenated coker-decomposed naphtha supplied to the catalytic reforming reactor is substantially free of silicon compounds. To achieve this, the hydrogenation catalyst must capture substantially all of the silicon compounds contained in the coker-decomposed naphtha.
[0005] Patent Document 1 describes that in the hydrogenation treatment of coker-cracked naphtha containing silicon compounds, supplying 0.01 to 10 volume percent of water together with the coker-cracked naphtha to the hydrogenation treatment catalyst improves the silicon collection ability of the hydrogenation treatment catalyst. [Prior art documents] [Patent Documents]
[0006] [Patent Document 1] U.S. Patent No. 6,576,121 [Overview of the Initiative] [Problems that the invention aims to solve]
[0007] As described above, the hydrogenation catalyst effectively reaches the end of its lifespan when it can no longer substantially capture all of the silicon compounds contained in the coker-cracked naphtha. Specifically, the measured silicon concentration in the product oil during the hydrogenation reaction is determined, and the hydrogenation catalyst reaches the end of its lifespan when this measured value exceeds a predetermined upper limit for silicon concentration in the product oil. On the other hand, when the measured value exceeds the upper limit, it means that silicon compounds have already flowed into the catalytic reforming reactor. Therefore, a method for estimating the silicon concentration in the product oil during the hydrogenation reaction is desired.
[0008] The present invention has been made in view of the above circumstances, and aims to provide an information processing method that can estimate the silicon concentration in the product oil discharged from the reactor outlet after a predetermined time has elapsed since the start of a reaction, in relation to a hydrogenation reaction carried out by flowing feed oil containing coker-cracked naphtha containing a silicon compound and hydrogen through a fixed-bed flow reactor filled with a catalyst, a silicon concentration calculation device that can estimate the silicon concentration, a silicon concentration calculation program for causing a computer to function as the silicon concentration calculation device, and a non-temporarily readable recording medium for a computer storing the program. [Means for solving the problem]
[0009] To solve the above problems, the present invention has the following aspects. [1] Regarding a hydrotreating reaction performed by flowing a feedstock oil containing coker cracked naphtha containing a silicon compound and hydrogen through a fixed-bed flow reactor filled with a catalyst, information 1 regarding the reaction rate of the silicon compound adsorption reaction of the catalyst, and any reaction t x Information 2 regarding the feedstock oil and information 3 regarding the operating conditions at the time of elapse of t days, and the reaction t x Another arbitrary reaction t before the elapse of t days x-1 An information acquisition step of acquiring information 4 regarding the silicon coating rate of the catalyst at the time of elapse of t days, and based on the acquired information 1, the information 2, the information 3, and the information 4, the reaction t x A silicon concentration calculation step of calculating information regarding the silicon concentration in the produced oil discharged from the reactor outlet at the time of elapse of t days, and an information processing method including the same. [2] The information 1 includes information regarding the reaction order, information regarding the activation energy, and information regarding the frequency factor, the information 2 includes information regarding the silicon concentration in the feedstock oil, and the information 3 includes information regarding the catalyst filling amount, information regarding the reaction temperature, and information regarding the feedstock oil supply amount. The information processing method according to [1]. [3] The silicon concentration calculation step calculates information regarding the silicon concentration in the produced oil based on the following formula 1. The information processing method according to [1] or [2]. [Number] In the above formula 1, Si P(t(x)) is the silicon concentration (mass ppm) in the produced oil at the time of elapse of t days, and Si x is the silicon concentration (mass ppm) in the feedstock oil at the time of elapse of t days, LHSV F(t(x)) is the liquid hourly space velocity (h x ) at the time of elapse of t days, and T (t(x)) is the reaction t x at the time of elapse of t days, and T -1 is the reaction t (t(x)) at the time of elapse of t days, and T xThe reaction temperature (K) after elapsed days is given by n, n is the reaction order of the silicon compound adsorption reaction of the catalyst, and Ea is the activation energy (J·mol) of the silicon compound adsorption reaction of the catalyst. -1 ) where A is the frequency factor of the silicon compound adsorption reaction of the catalyst, and R is the gas constant (J·mol). -1 ·K -1 ) and Si PB This is the silicon concentration (mass ppm) in the produced oil under standardized conditions, and Si FB This is the silicon concentration (mass ppm) in the feed oil under standardized conditions, and LHSV B This is the liquid space velocity (h) under standardized conditions. -1 ) and T B (t) is the reaction temperature (K) under standardized conditions. x -t x-1 ) ≤ 30 days, θ (t(x-1)) The above reaction t x-1 This is the silicon coating rate of the catalyst after several days, and is calculated using the following formula 2.
number
number
number
[0010] According to the present invention, in a hydrogenation reaction carried out by flowing feedstock oil containing coker-cracked naphtha containing silicon compounds and hydrogen through a fixed-bed flow reactor packed with a catalyst, it is possible to provide an information processing method that can estimate the silicon concentration in the product oil discharged from the reactor outlet after a predetermined time has elapsed since the start of the reaction, a silicon concentration calculation device that can estimate the silicon concentration, a silicon concentration calculation program for causing a computer to function as the silicon concentration calculation device, and a non-temporarily readable recording medium for a computer storing the program. [Brief explanation of the drawing]
[0011] [Figure 1] This is a flowchart of an information processing method according to one embodiment. [Figure 2] This is a flowchart of an information processing method according to one embodiment. [Figure 3] This is a flowchart of an information processing method according to one embodiment. [Figure 4] This is a block diagram of the silicon concentration calculation device according to one embodiment. [Figure 5]This figure shows the measured and estimated amounts of silicon deposited in each catalyst layer after 350 days of reaction in Example 1. [Modes for carrying out the invention]
[0012] The embodiments of the present invention will be described in detail below, but the following description is merely one 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 Methods The information processing method of this embodiment relates to a hydrogenation reaction carried out by flowing feedstock oil containing coker-cracked naphtha containing silicon compounds and hydrogen through a fixed-bed flow reactor packed with a catalyst, and includes information 1 regarding the reaction rate of the silicon compound adsorption reaction of the catalyst and an arbitrary reaction t x Information 2 regarding the feed oil and information 3 regarding the operating conditions as the days elapse, and the reaction t x Another arbitrary reaction t prior to the time elapsed t x-1 An information acquisition step (S1 in Figure 1) to acquire information 4 regarding the silicon coating rate of the catalyst after several days, and based on the acquired information 1, information 2, information 3, and information 4, the reaction t x The process includes a silicon concentration calculation step (S2 in Figure 1) which calculates information regarding the silicon concentration in the product oil discharged from the reactor outlet after several days.
[0014] The following describes each step. Note that each of the steps shown below is performed by, for example, the silicon concentration calculation device 1 of this embodiment. For example, S1 is performed by the acquisition unit 11, and S2 is performed by the calculation unit 13 in the computer body 12.
[0015] <Information Acquisition Steps> The information acquisition step of this embodiment involves acquiring information 1 regarding the reaction rate of the silicon compound adsorption reaction of the catalyst, and an arbitrary reaction t. x Information 2 regarding the feed oil and information 3 regarding the operating conditions as the days elapse, and the reaction t xAnother arbitrary reaction t prior to the time elapsed t x-1 This is a step to obtain information 4 regarding the silicon coating rate of the catalyst after several days have elapsed.
[0016] t x t x-1 t can be an integer or a decimal, and 0 ≤ t x-1 <t x x is an integer greater than or equal to 1, indicating that the information processing method of this embodiment was performed on the xth time after the reaction started. For example, t x If =0.5, it means 12 hours have passed since the start of the reaction. Also, t x t x-1 This can be in the past, present, or future from the time the information processing method of this embodiment is implemented. For example, the time the information processing method of this embodiment is implemented is two days after the reaction has started, and t x If the value is 4, it will estimate the silicon compound concentration two days later (in the future).
[0017] (Information 1) Information 1 is information regarding the reaction rate of the catalyst's silicon compound adsorption reaction. Examples of information regarding the reaction rate of the catalyst's silicon compound adsorption reaction include information regarding the catalyst's reaction rate constant, information regarding the reaction order of the catalyst's silicon compound adsorption reaction, information regarding the catalyst's activation energy, and information regarding the catalyst's frequency factor. Preferably, the information is information regarding the reaction order of the catalyst's silicon compound adsorption reaction, information regarding the catalyst's activation energy, and information regarding the catalyst's frequency factor.
[0018] Information regarding the reaction order of the silicon compound adsorption reaction of the catalyst, information regarding the activation energy of the catalyst, and information regarding the frequency factor of the catalyst can be obtained by methods known in this field. An example is described below.
[0019] • Reaction order of the silicon compound adsorption reaction of the catalyst Information regarding the reaction order of the silicon compound adsorption reaction of the catalyst can be determined by methods known in this art, based on the Arrhenius equation shown in Equation 5 below.
[0020]
number
[0021] Under constant conditions of liquid space velocity, reaction temperature, hydrogen partial pressure, hydrogen / raw material oil ratio, sulfur concentration in raw materials, and silicon concentration in raw materials, a hydrogenation reaction of raw material oil containing coker-cracked naphtha is carried out, and the silicon concentration in the resulting oil is measured. The reaction rate equation represented by equation 6 below shows the silicon concentration. F The silicon concentration in the raw material oil is Si P The silicon concentration in the resulting oil is substituted for the liquid-space velocity in LHSV. The result on the left side is plotted on the vertical axis, and 1 / LHSV is plotted on the horizontal axis. In this case, the vertical axis is a function of n.
[0022]
number
[0023] Under the above conditions, the same reaction is carried out by changing only the liquid space velocity, and the same plot is obtained. The same operation is performed for one type of liquid space velocity y, and one plot of y originating from one type of liquid space velocity y is obtained. Based on the obtained plot, a regression line is drawn passing through the origin, and a line represented by y=cx is obtained. y is [1 / (n-1){(1 / Si P n-1 )-(1 / Si F n-1 )}], where x is 1 / LHSV and c is k. Calculate the correlation function using Excel or similar software, and find the n that brings the correlation coefficient closest to 1. The resulting n is the reaction order. Note that n should be calculated to the order of one decimal place.
[0024] The above y1 is an integer greater than or equal to 3. A larger number of y1 values allows for obtaining a more accurate n. On the other hand, if the number of y1 values is too large, it takes a long time to obtain n, which is inefficient. In this embodiment, y1 is preferably between 3 and 10, and more preferably between 5 and 8.
[0025] When determining n, it is preferable to use reaction temperature, hydrogen partial pressure, hydrogen / raw material ratio, sulfur concentration in the raw material oil, and silicon concentration in the raw material oil that are in line with the actual operating conditions of the machine. Such reaction temperatures are, for example, 170-390°C, hydrogen partial pressure is 3.0-5.5 MPa, and hydrogen / raw material ratio is 400-2,000 [Nm³]. 3 The ratio is [ / kL], the sulfur concentration in the raw material oil is 1,000 to 15,000 ppm by mass, and the silicon concentration in the raw material oil is 0.1 to 40.0 ppm by mass. Similarly, it is preferable that the liquid space velocity for type y1 be set to conditions that are consistent with actual operating conditions. Such liquid space velocities are 0.1 to 2.0 h. -1 That is the case.
[0026] • Activation energy and frequency factors of the silicon compound adsorption reaction of the catalyst If we let the activation energy E in the Arrhenius equation represented by Equation 5 above be the activation energy Ea of the silicon compound adsorption reaction, and take the natural logarithm of both sides, we obtain the equation shown in Equation 7 below.
[0027]
number
[0028] Under constant conditions of liquid space velocity, reaction temperature, hydrogen partial pressure, hydrogen / raw material oil ratio, sulfur concentration in raw material, and silicon concentration in raw material, a hydrogenation reaction of raw material oil containing coker-cracked naphtha is carried out, and the silicon concentration in the resulting oil is measured. The silicon compound adsorption reaction rate equation represented by formula 6 is Si F The silicon concentration in the raw material oil is Si PThe reaction rate constant k is determined by substituting the silicon concentration in the resulting oil into LHSV, the liquid space velocity, and the reaction order obtained by the above method into n. The obtained reaction rate constant is substituted into equation 7, and the result on the left side (lnk) is plotted on the vertical axis and 1 / T on the horizontal axis.
[0029] Under the above conditions, the same reaction is carried out by changing only the reaction temperature, and the same plot is obtained. The same operation is performed for z1 reaction temperatures, and z1 of the above plots are obtained, each corresponding to z1 reaction temperature. A regression line is drawn based on the obtained plots, and its slope is determined. Since this slope is Ea / R, the activation energy Ea of the silicon compound adsorption reaction can be determined by subtracting R from the slope. Furthermore, since the intercept is lnA, the frequency factor A of the catalyst's silicon compound adsorption reaction can be determined.
[0030] The above z1 is an integer greater than or equal to 3. A larger number of z1 values allows for more accurate Ea and A. On the other hand, if the number of z1 values is too large, it takes too long to obtain Ea and A, making it inefficient. In this embodiment, z1 is preferably between 3 and 10, and more preferably between 5 and 8.
[0031] When determining Ea and A, it is preferable that the reaction temperature, hydrogen partial pressure, hydrogen / raw material ratio, sulfur concentration in the raw material, and silicon concentration in the raw material are conditions that correspond to the actual operating conditions of the machine. Examples of such conditions include those described in the section on determining n.
[0032] (Information 2) Information 2 is any reaction t x This information pertains to the raw material oil over time. Examples of raw material oil information include information on the composition of the raw material oil, and examples of raw material oil composition information include information on the silicon concentration in the raw material oil and information on the sulfur concentration in the raw material oil. Preferably, the information pertains to the silicon concentration in the raw material oil.
[0033] Information regarding the silicon concentration in the raw material oil can be obtained using silicon concentration measurement methods known in this field, such as inductively coupled plasma mass spectrometry (ICP-MS) or X-ray fluorescence analysis. Furthermore, the silicon concentration in the raw material oil can be controlled by changing the raw material oil. It is preferable that the information regarding the silicon concentration in the raw material oil be a set value; that is, the silicon concentration of the raw material oil intended for use can be used.
[0034] Information regarding the sulfur concentration in the raw material oil can be obtained using sulfur concentration measurement methods known in this field, such as ultraviolet fluorescence spectroscopy or wavelength-dispersive X-ray fluorescence spectroscopy. Furthermore, the sulfur concentration in the raw material oil can be controlled by changing the raw material oil. It is preferable that the information regarding the sulfur concentration in the raw material oil be a set value; that is, the sulfur concentration of the raw material oil intended for use can be used.
[0035] (Information 3) Information 3 is any reaction t x This information pertains to the operating conditions during the course of the process. Examples of information pertaining to the operating conditions include information on the catalyst charge amount, reaction temperature, feedstock supply amount, hydrogen partial pressure, and hydrogen supply amount, with the catalyst charge amount, reaction temperature, and feedstock supply amount being preferred. Furthermore, the operating conditions include the aforementioned t x day, t x-1 This also includes time information such as the date.
[0036] Information on the catalyst filling amount, information on the reaction temperature, information on the supply amount of the feedstock oil, information on the hydrogen partial pressure, and information on the supply amount of hydrogen can be obtained by methods known in the art. Information on the catalyst filling amount, information on the reaction temperature, information on the supply amount of the feedstock oil, information on the hydrogen partial pressure, and information on the supply amount of hydrogen can be controlled in a hydrotreating reaction in which a feedstock oil containing coker cracked naphtha containing a silicon compound and hydrogen are circulated through a fixed-bed flow reactor filled with a catalyst. It is preferable that the information on the operating conditions is a set value. That is, it is preferable to use the planned operating conditions.
[0037] (Information 4) Information 4 is the reaction t x at any other arbitrary reaction t before the elapse of the day x-1 and is information on the silicon coating rate of the catalyst at the elapse of the day. In the present specification, the "silicon coating rate of the catalyst" means the ratio of the amount of silicon deposition per 1 g of the catalyst to the maximum amount of silicon deposition per 1 g of the catalyst.
[0038] The maximum amount of silicon deposition per 1 g of the catalyst (unit: mass %, hereinafter also referred to as "C" Si∞ ) is a value specific to the catalyst and can be obtained by methods known in the art. As an example of the method for obtaining C Si∞ , for example, in a full-scale or bench-scale unit, the reaction is carried out at the reaction temperature, LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, silicon concentration, and sulfur concentration of the assumed full-scale operating conditions. Then, the silicon concentration in the produced oil is analyzed over time. Since the silicon compound deposits on the catalyst, at the beginning of the reaction, "silicon concentration in the feedstock oil > silicon concentration in the produced oil", but the silicon concentration in the produced oil gradually increases, and finally, "silicon concentration in the feedstock oil = silicon concentration in the produced oil". When "silicon concentration in the feedstock oil = silicon concentration in the produced oil", the reaction is stopped, the catalyst is withdrawn, the silicon concentration in the catalyst is measured, and the obtained value is taken as C Si∞ . The silicon concentration in the catalyst can be measured by inductively coupled plasma-atomic emission spectrometry (ICP-AES) or atomic absorption spectrometry (AAS).
[0039] C Si∞ may have temperature dependence depending on the catalyst. The presence or absence of temperature dependence can be determined by the following method. The above C Si∞ is obtained by performing the method of obtaining C at different reaction temperatures, and each C Si∞ is obtained. Plot the reaction temperature (K) on the horizontal axis and C Si∞ on the vertical axis to obtain an equation represented by y = ax + b. When a = 0, it can be determined that C Si∞ has no temperature dependence, and b is defined as C Si∞ . When a ≠ 0, a becomes the term indicating the temperature dependence of C Si∞ . In this case, ax + b is defined as C Si∞ (x is the reaction temperature). Hereinafter, b is also referred to as C Si∞(0) .
[0040] <Silicon concentration calculation step> The silicon concentration calculation step is a step of calculating information on the silicon concentration in the produced oil discharged from the reactor outlet at the time of reaction passage based on the above information 1, the above information 2, the above information 3, and the above information 4. tx
[0041] As described above, there is a unique C Si∞ in the catalyst. Therefore, assuming that all silicon compounds in the feedstock oil are deposited on the catalyst, theoretically, when the total amount of silicon (g) in the feedstock oil supplied to the catalyst layer exceeds " Si∞ (g / 1g) × catalyst filling amount (g)", it should be detected in the produced oil at the reactor outlet, and the silicon concentration in the subsequent produced oil should be equal to the silicon concentration in the feedstock oil.
[0042] However, according to the study by the inventor of the present application, it has been found that the silicon concentration in the produced oil cannot be accurately estimated only by the above theoretical calculation. The reason for this may be that the above theory does not consider information on the reaction rate of the silicon compound adsorption reaction of the catalyst. For example, the silicon compound adsorption reaction is affected by the above information 2 on the silicon concentration in the feedstock oil, the above information 3 such as the reaction temperature and the liquid hourly space velocity, and the above information 4 on the silicon coating rate of the catalyst.
[0043] The inventors of this invention have found that by considering information regarding the reaction rate of the silicon compound adsorption reaction, it is possible to estimate the silicon concentration in the resulting oil with high accuracy.
[0044] That is, the information 1, the information 2, the information 3, the information 4, and the corresponding reaction t x The measured silicon concentration in the produced oil over time is used as a dataset, and machine learning such as deep learning using the dataset, or regression analysis commonly used in this technology, is used to generate a reaction t based on the information 1, information 2, information 3, and information 4. x It is possible to generate a function that can calculate the measured silicon concentration in the generated oil over time. Based on such a function, the reaction tx This allows for the calculation of information regarding the silicon concentration in the generated oil discharged from the reactor outlet after several days.
[0045] The inventors of this application have used the information 1, the information 2, the information 3, the information 4, and the corresponding reaction t xThe function was investigated based on the measured silicon concentration in the product oil over time. As a result, it was found that the sulfur concentration in the feed oil in Information 2 had almost no effect on the silicon concentration in the product oil discharged from the reactor outlet. On the other hand, it was found that the silicon concentration in the feed oil in Information 2 had a significant effect on the silicon concentration in the product oil discharged from the reactor outlet. Furthermore, it was found that the information regarding hydrogen partial pressure and hydrogen supply in Information 3 had almost no effect on the silicon concentration in the product oil discharged from the reactor outlet. On the other hand, it was found that the information regarding catalyst loading amount, reaction temperature, and feed oil supply in Information 3 had a significant effect on the silicon concentration in the product oil discharged from the reactor outlet. As a result of these investigations, the inventors of this application found a function (equation) as shown in Equation 1 below. However, the following function (formula) is merely an example, and other information 2 (such as sulfur concentration in the feed oil) and information 3 (information regarding hydrogen partial pressure and hydrogen supply) may be added to the following function (formula). Furthermore, in the following function (formula), information 1 is used to describe the reaction order of the silicon compound adsorption reaction of the catalyst, the activation energy of the catalyst, and the frequency factor of the catalyst, but for example, information 1 could be used to describe the reaction rate constant of the catalyst, resulting in a different function (formula).
[0046] In one embodiment of the present invention, the silicon concentration calculation step is preferably performed by calculating information regarding the silicon concentration in the generated oil based on the following formula 1.
number
[0047] n, Ea, and A are the aforementioned information 1. Si F(t(x)) This is the aforementioned information 2. LHSV (t(x)) , T (t(x)) This is the information 3 mentioned above. Furthermore, LHSV can be determined by dividing the supply rate of raw material oil (volume / h) by the catalyst filling rate (volume). θ (t(x-1)) This is the aforementioned information 4.
[0048] Si PB Si FB LHSV B , T B is a constant (hereinafter also called a standardized constant). A standardized constant is, for example, Si P(t(x)) The Si concentration in the produced oil is the same as the silicon concentration measured in the actual product. PB Si FB LHSV B , T B It can be found as a combination of these.
[0049] Furthermore, standardized constants can also be determined by the following method. The reaction is carried out using the catalyst packing configuration and feedstock oil of the assumed actual operating conditions. In this case, the reaction temperature, LHSV, and silicon concentration in the feedstock oil are set so that silicon can be detected in the product oil in the initial stages of the reaction. Specifically, the reaction temperature is set lower than the assumed actual operating conditions, the LHSV is set higher than the assumed actual operating conditions, and the silicon concentration in the feedstock oil is set higher than the assumed actual operating conditions. The initial stages of the reaction are, for example, 0.1 to 1 day after the start of the reaction. The silicon concentration in the product oil is, for example, 0.2 to 5.0 ppm by mass. The reaction temperature may be, for example, 0.8 to 1.2 times (in °C) the reaction temperature of the assumed actual operating conditions, and the LHSV may be 0.5 to 2.0 times the LHSV of the assumed actual operating conditions. The silicon concentration in the initial generated oil is Si PB , the reaction temperature is T B , LHSV to LHSV B The silicon concentration in the raw material oil is Si FB That is also acceptable.
[0050] (t x -t x-1 ) is preferably 30 days or less, more preferably 7 days or less, and even more preferably 1 day or less. If the total reaction period is y days, (t x -t x-1 ) is preferably y / 43 to y / 42 days, more preferably y / 186 to y / 163 days, and even more preferably y / 1,300 to y / 650 days. (t x -t x-1 ) essentially means the interval at which the information processing method of this embodiment is performed. If this interval is less than or equal to the upper limit, the accuracy of the information 4 is improved, and the precision of the obtained silicon concentration is improved.
[0051] Si F(t(x)) LHSV (t(x)) , T (t(x))If one or more of the following are changed, it is preferable to perform the silicon concentration calculation step, that is, the calculation of the silicon concentration in the generated oil, based on formula 1, immediately before the change. That is, reaction t x-1 After several days ~ reaction t x Si F(t(x)) LHSV (t(x)) , T (t(x)) It is preferable to keep this constant.
[0052]
number
[0053] Note C Si∞ If it does not have temperature dependence, then the above C Si∞(0) C in the above formula 2 Si∞ It is used as such. On the other hand, C Si∞ If it is temperature-dependent, use the above a and Si∞, and aT (t(x)) +C Si∞(0) C in the above formula 2 Si∞ To use as such.
[0054]
number
[0055] Also, C Si(t(x-2)) Similarly, this can be determined by the above formula 8. That is, in the above formula 8, C Si(t(x-1)) to C Si(t(x-2)) It can be calculated as follows. In other words, C is the amount of silicon deposited per gram of catalyst at the start of the reaction (g). Si(0) By repeatedly calculating the above equation 8 from the value, C Si(t(x-1)) It is possible to find C Si(0) This is the amount of silicon deposited per gram of fresh catalyst (g), which is usually 0, but if the fresh catalyst contains silicon as an impurity, the amount of impurity per gram of catalyst (g) is set to C Si(0) It can be done this way.
[0056] (When there are two or more catalyst layers) There may be two or more types of catalysts packed into the reaction tube (two or more catalyst layers). If the types of catalysts are different, then Information 1 and Information 4 will be different. Also, if the amount of catalyst packed into each catalyst layer is different, then the liquid space velocity (Information 3) will be different. Even when only one type of catalyst is used (one catalyst layer), the reaction temperature (information 3 above) may differ depending on the position of the catalyst layer. Furthermore, the silicon concentration in the feedstock oil also differs depending on the position of the catalyst layer (silicon concentration in the feedstock oil at the reactor inlet ≥ silicon concentration in the feedstock oil at the reactor outlet). If there are two or more types of catalysts packed into the reaction tube (two or more catalyst layers), the silicon concentration in the generated oil should be calculated for each catalyst layer based on the above formula 1, and the silicon concentration in the generated oil in the catalyst layer closest to the outlet of the reactor should be calculated. If the reaction temperature (information 3) differs depending on the position of the catalyst layer, the silicon concentration in the produced oil should be calculated based on formula 1 for each catalyst layer with substantially the same reaction temperature, and the silicon concentration in the produced oil at the catalyst layer closest to the outlet of the reactor should be calculated. Also, since the silicon concentration in the feedstock oil (information 2) differs depending on the position of the catalyst layer, the silicon concentration in the produced oil should be calculated based on formula 1 for each catalyst layer, and the silicon concentration in the produced oil at the catalyst layer closest to the outlet of the reactor should be calculated. The following provides a detailed explanation.
[0057] Specifically, the silicon concentration calculation step preferably involves calculating information regarding the silicon concentration in the generated oil based on the following formula 9.
number
[0058] In the above equation 9, when d=1 (in the case of the catalyst layer at the inlet of the reactor), Si F(t(x))[d] This is the Si in formula 1. F(t(x)) On the other hand, if d≧2, Si F(t(x))[d] is, Si P(t(x))[d-1] That is. Si P(t(x))[d-1] The above reaction t x This is the silicon concentration (mass ppm) in the generated oil at the outlet of the d-1 layer catalyst layer after 1 day has elapsed. P(t(x))[d-1] Similarly, this can be determined by the above formula 9. That is, in the above formula 9, Si P(t(x))[d] to Si P(t(x))[d-1] This can be determined as follows: In other words, in this embodiment, when d≧2, the silicon concentration in the generated oil at the outlet of the preceding catalyst layer is used as the silicon concentration in the raw material oil at the catalyst layer inlet.
[0059] n, Ea [d] , A [d] This is the aforementioned information 1. Si F(t(x))[d] This is the aforementioned information 2. LHSV (t(x))[d] , T (t(x))[d] This is the information 3 mentioned above. Furthermore, LHSV can be determined by dividing the supply rate of raw material oil (volume / h) by the catalyst filling rate (volume). θ (t(x-1))[d] This is the aforementioned information 4.
[0060] Si PB Si FB LHSV B , T B As mentioned above, this is a constant. Furthermore, the same value is used for all catalyst layers. The standardized constant is, for example, Si when d has the largest value (d=d(MAX)). P(t(x))[d(MAX)] The Si concentration in the produced oil is the same as the silicon concentration measured in the actual product. PB Si FB LHSV B , T B It can be found as a combination of these.
[0061] Furthermore, standardized constants can also be determined by the following method. The reaction is carried out using the catalyst packing configuration and feedstock oil of the assumed actual operating conditions. In this case, the reaction temperature, LHSV, and silicon concentration in the feedstock oil are set so that silicon can be detected in the product oil in the initial stages of the reaction. Specifically, the reaction temperature is set lower than the assumed actual operating conditions, the LHSV is set higher than the assumed actual operating conditions, and the silicon concentration in the feedstock oil is set higher than the assumed actual operating conditions. The initial stages of the reaction are, for example, 0.1 to 1 day after the start of the reaction. The silicon concentration in the product oil is, for example, 0.2 to 5.0 ppm by mass. The reaction temperature may be, for example, 0.8 to 1.2 times the reaction temperature of the assumed actual operating conditions (in °C), and the LHSV may be 0.5 to 2.0 times the LHSV of the assumed actual operating conditions. The silicon concentration in the initial generated oil is Si PB , the reaction temperature is T B , LHSV to LHSV B The silicon concentration in the raw material oil is Si FB This may also be done. Furthermore, the above Si P(t(x))[d] , T (t(x))[d] LHSV (t(x))[d] Si F(t(x))[d] These are values per catalyst layer, but the standardized constant uses the values for all catalyst layers combined.
[0062] (t x -t x-1 ) is preferably 30 days or less, more preferably 7 days or less, and even more preferably 1 day or less. If the total reaction period is y days, (t x -t x-1 ) is preferably y / 43 to y / 42 days, more preferably y / 186 to y / 163 days, and even more preferably y / 1,300 to y / 650 days. (t x -t x-1 ) essentially means the interval at which the information processing method of this embodiment is performed. If this interval is less than or equal to the upper limit, the accuracy of the information 4 is improved, and the precision of the obtained silicon concentration is improved.
[0063] SiF(t(x))[d] LHSV (t(x))[d] , T (t(x))[d] If one or more of the following are changed, it is preferable to perform the silicon concentration calculation step, that is, the calculation of the silicon concentration in the produced oil, based on formula 9, immediately before the change. That is, reaction t x-1 After several days ~ reaction t x Si F(t(x))[d] LHSV (t(x))[d] , T (t(x))[d] It is preferable to keep this constant.
[0064]
number
[0065] Note C Si∞[d] If it does not have temperature dependence, then the above C Si∞(0) C in the above formula 10 Si∞ It is used as such. On the other hand, C Si∞[d] If it is temperature-dependent, use the above a and Si∞, and aT (t(x))[d] +C Si∞(0) C in the above formula 10 Si∞[d] To use as such.
[0066] In the above formula 10, C Si(t(x-1))[d] This is calculated by formula 11 below.
[0067]
number
[0068] Also, C Si(t(x-2))[d] Similarly, this can be determined by the above formula 11. That is, in the above formula 11, C Si(t(x-1))[d] to C Si(t(x-2))[d] It can be calculated as follows. In other words, C is the amount of silicon deposited per gram of catalyst in the d-th catalyst layer at the start of the reaction. Si(0)[d] By repeatedly calculating the above formula 11 from the value of C, Si(t(x-1))[d] It is possible to find C Si(0)[d] C is the amount of silicon deposited per gram of fresh catalyst in the d-th catalyst layer, which is usually 0. However, if the fresh catalyst contains silicon as an impurity, the amount of the impurity per gram of catalyst (g) is set to C. Si(0)[d] It can be done this way.
[0069] For all catalyst layers in the d layer, the silicon concentration calculation step is performed based on the above equation 9, and the Si concentration is calculated when d has the largest value (d=d(MAX)). P(t(x))[d(MAX)] ga reaction t x This represents the silicon concentration in the product oil discharged from the reactor outlet after several days.
[0070] Measured silicon concentration (Si) P(obs) The silicon concentration Si obtained by the information processing method of this embodiment P(t(x)) (Si P(t(x))[d(MAX)] The proportion of Si (including) P(t(x)) / Si P(obs) The Si value is preferably 0.70 to 1.30, and more preferably 0.95 to 1.05. P(t(x)) / Si P(obs) If the value falls within the aforementioned range, it can be determined that the silicon concentration in the generated oil can be estimated with high accuracy.
[0071] ≪Information Output Step≫ The system may further include an information output step (S3 in Figure 1) for outputting information regarding the silicon concentration obtained in this manner. For example, S3 is performed by the output unit 14.
[0072] ≪Hydrogenation reaction of feedstock oil containing coker-cracked naphtha≫ This document outlines the hydrogenation reaction of feedstock oil containing coker-cracked naphtha. Coker-cracked naphtha is a fraction obtained by thermally decomposing vacuum distillation residue oil in a coker unit, with an initial boiling point of 30°C or higher and an endpoint of 200°C or lower. The density of coker-cracked naphtha is 0.700-0.750 g / cm³. 3 The content of coker-cracked naphtha in the raw material oil may be, for example, 5% by volume or more, or 70% by volume or more. Other types of oils included in the raw material oil, besides coker-cracked naphtha, include atmospheric distillation naphtha and fluid catalytic cracking naphtha.
[0073] The hydrogenation reaction of feedstock oil containing coker-cracked naphtha can be carried out by contacting the feedstock oil containing coker-cracked naphtha with a hydrogenation catalyst in the presence of hydrogen. The hydrogenation catalyst is not particularly limited, and any hydrogenation catalyst known in this art can be used. Various materials can be used as catalyst supports, such as silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, 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, with alumina being particularly preferred, and γ-alumina being particularly preferred among aluminas. These inorganic oxides may be used individually or in combination of two or more.
[0074] The metal to be included as an active component in the support 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 metallic form, metal oxide, or metal sulfide, and may also exist in a form where the metal is bonded to the catalyst support by ion exchange or the like. The content of this metal component is usually in the range of about 1 to 25 mass%, based on the catalyst and in terms of oxides. If the metal content is less than 1 mass%, the absolute amount of metal acting as active sites is small, and hydrogenation activity, including desulfurization activity (hereinafter simply referred to as hydrogenation activity), will not be exhibited. Conversely, if the content of the supported metal is too much more than 25 mass%, metal aggregation occurs, reducing the number of active sites, and as a result, the hydrogenation activity actually decreases. Furthermore, if necessary, in addition to the active metals consisting of Group 6 and Group 8 of the periodic table, phosphorus, boron, zinc, zirconia, etc. can be included. When applying the method of the present invention, there are no restrictions on the form of the catalyst layer, and it can be applied to reactors with catalyst layers such as fixed beds, moving beds, and fluidized beds. The specific surface area of the hydrogenation catalyst is 150-420 m². 2 It is preferable that the amount be / g, and 170-400m 2 It is more preferable that the amount be / g, and 190-380m 2 It is even more preferable that it be / g.
[0075] The conditions for the hydrogenation reaction of feedstock oil containing coker-cracked naphtha are generally a reaction temperature of 170-390°C, preferably 200-360°C, a hydrogen partial pressure of 3.0-5.5 MPa, preferably 3.5-5.0 MPa, and an LHSV of 0.1-15.0 hr. -1 Preferably 0.5 to 3.5 hours -1 The hydrogen / raw material ratio is 400-2,000 [Nm³]. 3 [kL], preferably 600-1,800 [Nm 3 It is [ / kL].
[0076] The sulfur concentration in the feed oil containing coker-cracked naphtha is typically 1,000 to 15,000 ppm by mass. The sulfur concentration in the resulting oil is typically 0.1 to 0.5 ppm by mass or less. The silicon concentration in the feed oil containing coker-cracked naphtha is typically 0.1 to 40.0 ppm by mass.
[0077] ≪Silicon Concentration Calculation Device≫ The silicon concentration calculation device of this embodiment relates to a hydrogenation treatment reaction in which feedstock oil containing coker-cracked naphtha containing silicon compounds and hydrogen are passed through a fixed-bed flow reactor filled with a catalyst, and provides information 1 regarding the reaction rate of the silicon compound adsorption reaction of the catalyst and an arbitrary reaction t x Information 2 regarding the feed oil and information 3 regarding the operating conditions as the days elapse, and the reaction t x Another arbitrary reaction t prior to the time elapsed t x-1 An acquisition unit acquires information 4 regarding the silicon coating rate of the catalyst as the days have elapsed, and based on the information 1, information 2, information 3, and information 4 acquired by the acquisition unit, the reaction t xThe silicon concentration calculation device of this embodiment includes a calculation unit that calculates information regarding the silicon concentration in the generated oil discharged from the reactor outlet after several days.
[0078] The silicon concentration 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 silicon concentration calculation device 1 may be configured using one or more information processing devices. For example, the silicon concentration calculation device 1 may be constructed as a cluster machine, as a cloud, or in any other manner. The silicon concentration calculation device 1 has, for example, an acquisition unit 11 and a computer body 12 that processes information from the acquisition unit, as shown in Figure 4. The silicon concentration calculation device 1 may also have an output unit 14 that outputs the information processed by the computer 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). Furthermore, some or all of these components may be realized 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 the cooperation of software and hardware. The program may be stored in advance on a storage device such as an HDD (Hard Disk Drive) or flash memory (a storage device equipped with a non-transient storage medium), or it may be stored on a removable storage medium such as a DVD or CD-ROM (a non-transient storage medium) and installed on the storage device when the storage medium is inserted into the drive device. The storage device consists of, for example, an HDD, flash memory, EEPROM (Electrically Erasable Programmable Read Only Memory), ROM (Read Only Memory), or RAM (Random Access Memory).
[0079] The acquisition unit 11 receives predetermined information from the reaction operator and transmits the acquired information to the computer unit 12. The information acquired by the acquisition unit 11 in this embodiment concerns a hydrogenation reaction carried out by flowing feedstock oil containing coker-cracked naphtha containing silicon compounds and hydrogen through a fixed-bed flow reactor filled with a catalyst, and includes information 1 regarding the reaction rate of the silicon compound adsorption reaction of the catalyst and an arbitrary reaction t x Information 2 regarding the feed oil and information 3 regarding the operating conditions as the days elapse, and the reaction t x Another arbitrary reaction t prior to the time elapsed t x-1 Information 4 concerns the silicon coating rate of the catalyst as the number of days elapsed. Information 1, Information 2, Information 3, and Information 4 are as described above. For example, the acquisition unit 11 performs the information acquisition step described above. The acquisition unit 11 only needs to acquire Information 1, Information 2, Information 3, and Information 4, and there are no particular limitations on the method of acquisition.
[0080] In this embodiment, the acquisition unit 11 is configured as a single keyboard. The specific configuration of the acquisition unit 11 is not limited; in this embodiment, it is a keyboard, but it may also be a touch panel or the like. Furthermore, acquisition units for acquiring various types of information may be configured separately and each may be independently connected to the computer main unit 12. Also, the acquisition unit 11 may be configured to directly acquire the aforementioned information via wired or wireless connection from a computer used for controlling reactors, etc.
[0081] The main unit 12 is, for example, a so-called computer capable of processing various types of information. The computer body 12 includes an arithmetic unit 13. For example, a predetermined program is incorporated into the computer body 12, and the arithmetic unit 13 is functionally configured by the execution of this program. Specifically, in this calculation unit 13, based on the information 1, information 2, information 3, and information 4 acquired by the acquisition unit 11, the response t xThe silicon concentration in the generated oil discharged from the reactor outlet after several days is calculated. For example, the calculation unit 13 performs the silicon concentration calculation step described above. The calculation unit 13 may include, for example, a processor such as a CPU (Central Processing Unit) or MPU (Micro Processing Unit) and non-volatile or volatile semiconductor memory (for example, RAM (Random Access Memory), ROM (Read Only Memory), flash memory, EPROM (Erasable Programmable Read Only Memory), EEPROM (Electrically Erasable Programmable Read Only Memory)). For example, the calculation unit 13 may be a microcontroller such as an MCU.
[0082] The calculation unit 13 calculates the t as described above. x Information regarding the silicon concentration in the generated oil discharged from the reactor outlet after several days may be output to the output unit 14.
[0083] The output unit 14 receives the calculation result (silicon concentration) output by the computer main unit 12 (specifically, the calculation unit 13) and outputs the received calculation result to an external device. In this embodiment, the output unit 14 is composed of a display unit such as a CRT display, liquid crystal 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 for controlling the hydrogenation reaction of raw material oil containing coker cracked naphtha). The output unit 14 may also be a combination of these. For example, the output unit 14 performs the information output step described above.
[0084] Furthermore, this embodiment provides a silicon concentration calculation program for enabling a computer to function as a silicon concentration calculation device, and a non-temporarily readable recording medium for the computer that stores the program. Examples of non-temporarily readable recording media for the computer include magnetic tape (such as digital data storage (DSS)), magnetic disks (such as hard disk drives (HDD) and flexible disks (FD)), optical disks (such as compact discs (CD), digital versatile discs (DVD), and Blu-ray discs (BD)), magneto-optical disks (MO), and flash memory (such as SSDs (Solid State Drives), memory cards, and USB memory).
[0085] <Information processing method and method for utilizing silicon concentration calculation device> According to the information processing method and silicon concentration calculation device of this embodiment, in a hydrogenation reaction carried out by flowing feedstock oil containing coker-cracked naphtha containing silicon compounds and hydrogen through a fixed-bed flow reactor filled with a catalyst, it is possible to estimate the silicon concentration in the resulting oil after a predetermined time has elapsed since the start of the reaction. According to the information processing method and silicon concentration calculation device of this embodiment, it is possible to obtain a time-series plot of the estimated silicon concentration. The following applications can be considered from the relationship between the plot and the set upper limit of the silicon concentration in the resulting oil.
[0086] The first application is to estimate the operating time (number of days) required to replace the catalyst. Such information processing methods are shown in S3-1 and S4 or S3-1 and S4-1 in Figure 2. The information processing method shown in S3-1 and S4-1 in Figure 2 consists of a step of comparing information on the silicon concentration calculated in the silicon concentration calculation step (S2 in Figure 1) with the set upper limit of the silicon concentration in the generated oil (S3-1 in Figure 2), and if the information on the silicon concentration exceeds the set upper limit of the silicon concentration, the reaction t xThe information processing method shown in S3-1 and S4 of Figure 2 includes an information output step (S4-1 in Figure 2) that outputs the elapsed time in days as information regarding the catalyst life. The information processing method includes a step (S3-1 in Figure 2) that compares the silicon concentration information calculated in the silicon concentration calculation step (S2 in Figure 1) with the set upper limit value of the silicon concentration in the generated oil, and an information output step (S4 in Figure 2) that outputs the calculated silicon concentration information if the silicon concentration information is less than or equal to the set upper limit value of the silicon concentration. Each of the above steps is performed, for example, by the silicon concentration calculation device 1 of this embodiment. For example, S3-1 is performed by the calculation unit 13 in the computer body 12, and S4 and S4-1 are performed by the output unit 14. The upper limit value for the silicon concentration in the generated oil may be stored in advance in the calculation unit 13 in the computer body 12. An example of an upper limit value for the silicon concentration in the generated oil is 0.1 ppm by mass.
[0087] A second application is to estimate the reaction conditions (processing rate (LHSV), etc.) required to achieve a predetermined operating time. This information processing method is represented by S1A to S2A in Figure 3. The information processing method shown in S1A and S2A in Figure 3 is used for any reaction t x The process includes an information acquisition step (S1A in Figure 3) for acquiring information on the silicon concentration in the product oil discharged from the target reactor outlet after several days, and a reaction condition calculation step (S2A in Figure 2) for calculating information 1, information 2, information 3, and information 4 based on the acquired information on the target silicon concentration. It may further include an information output step (S3A in Figure 3) for outputting the information 1, information 2, information 3, and information 4 obtained in this way. Specifically, for example, when using formula 1, the Si of formula 1 P(t(x)) Substitute the information regarding the target silicon concentration into S such that the equation in Equation 1 holds true. P(t(x)) LHSV (t(x)) , T (t(x)) , θ (t(x-1)) We just need to find the combination of θ. (t(x-1)) To adjust reaction t x-1The silicon concentration in the raw material oil, the liquid space velocity, and the reaction temperature may be adjusted before the day has elapsed. Each of the above steps is performed, for example, by the reaction temperature calculation device 1 of this embodiment. For example, S1A is performed by the acquisition unit 11, S2A is performed by the calculation unit 13 in the computer body 12, and S3A is performed by the output unit 14. The silicon concentration in the produced oil discharged from the target reactor outlet may be stored in advance in the calculation unit 13 in the computer body 12. [Examples]
[0088] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
[0089] [Example 1] For a catalyst used in the hydrogenation treatment of feedstock oil containing coker-cracked naphtha containing silicon compounds, Si∞ was determined by the method described above. The result showed that Si∞ did not exhibit temperature dependence and was 10 (g / 1g of catalyst). Furthermore, n, Ea, and A were determined by the method described above. The results were n = 1.2, Ea = 70.0 (kJ / mol), and A = 0.15. In addition, Si PB Si FB LHSV B , T B The result was obtained using the method described above. PB is 0.2 (mass ppm), Si FB is 30 (mass ppm), LHSV B is 2.5(h -1 ), T B The temperature was 260°C.
[0090] The reaction was carried out in an actual reactor using the same feedstock oil and catalyst used to determine the parameters mentioned above. Specifically, 60.0 g of the catalyst was packed into a fixed-bed flow reactor. A hydrogenation reaction was carried out by flowing feedstock oil containing 50 vol% coker-cracked naphtha and hydrogen through the fixed-bed flow reactor. Throughout the entire reaction period, the reaction conditions were set to a silicon concentration of 5.0 (mass ppm) in the feedstock oil and an LHSV of 1.46 (h -1The supply amount of raw material oil was set to 87.6 g / h, and the reaction temperature was set to 320°C. As a silicon concentration calculation step, information regarding the silicon concentration in the produced oil was calculated based on Equation 9. The catalyst layer was evenly divided into 45 layers, and for each layer, Si was calculated based on Equation 9. P(t(x))[d] Calculate Si P(t(x))
[45] react t x This was calculated as the silicon concentration in the product oil discharged from the reactor outlet after several days. Estimated silicon concentration in the product oil after 330-350 days from the start of the reaction (Si P(t(x))
[45] The estimated and measured values are shown in Table 1. The reaction was stopped 350 days after the start of the reaction. After stopping, the catalyst from each layer was removed and the amount of silicon deposited on the catalyst was measured. The estimated and measured values of the silicon deposited on the catalyst after 350 days are shown in Figure 1.
[0091] [Table 1] As shown in Table 1, virtually no silicon was detected at the reactor outlet until 350 days had elapsed. Furthermore, as shown in Figure 1, the estimated and measured silicon deposition amounts of the catalyst were in good agreement. Specifically, the measured silicon deposition amount C per gram of catalyst was... Si(t(x-1))[d](obs) The measured silicon deposition amount C per gram of catalyst, which can be determined by the information processing method of this embodiment, is Si(t(x-1))[d] The ratio C Si(t(x-1))[d] / C Si(t(x-1))[d](obs) The values ranged from 0.98 to 1.18 (d=10, 20, 30, 40). As mentioned above, the silicon deposition amount of the catalyst is C Si(t(x-1))[d] This is calculated by formula 11, etc. Formula 11 contains Si P(t(x-1)[d]) Because it includes C Si(t(x-1))[d] is, Si P(t(x-1)[d]) It depends on C. Si(t(x-1))[d] The high precision of Si P(t(x-1)[d]) This also means that the accuracy is high. [Industrial applicability]
[0092] The information processing method according to the present invention is useful because it can estimate the silicon concentration in the resulting oil after a predetermined time has elapsed since the start of a hydrogenation reaction of a feed oil containing coker-cracked naphtha containing silicon compounds. [Explanation of symbols]
[0093] 1. Silicon concentration calculation device 11...Acquisition part 12...Calculator body 13... Arithmetic section 14.. Output section
Claims
1. Regarding a hydrogenation reaction carried out by passing feedstock oil containing coker-cracked naphtha containing silicon compounds and hydrogen through a fixed-bed flow reactor packed with a catalyst, Information 1 regarding the reaction rate of the silicon compound adsorption reaction of the catalyst, and an arbitrary reaction t ｘ Information 2 regarding the feedstock oil and information 3 regarding the operating conditions as the days elapse, and the reaction t ｘ Another arbitrary reaction t prior to the time elapsed t ｘ－１ An information acquisition step to acquire information 4 regarding the silicon coating rate of the catalyst after several days, Based on the acquired information 1, information 2, information 3, and information 4, the reaction t ｘ An information processing method comprising: a silicon concentration calculation step of calculating information regarding the silicon concentration in the product oil discharged from the reactor outlet after several days; The information 1 is the reaction order of the silicon compound adsorption reaction of the catalyst, the activation energy of the silicon compound adsorption reaction of the catalyst, and the frequency factor of the silicon compound adsorption reaction of the catalyst. The information 2 above is the silicon concentration in the raw material oil after the reaction t has elapsed for x days. The information 3 is the liquid space velocity at the time t x days have elapsed since the reaction, and the reaction temperature at the time t x days have elapsed since the reaction. The information 4 above is the silicon coating rate of the catalyst after reaction t x-1 days have elapsed. Information regarding the silicon concentration in the generated oil is the silicon concentration in the generated oil after reaction t x days have elapsed. The silicon concentration calculation step is an information processing method that calculates information regarding the silicon concentration in the generated oil based on the following formula 1. [Math 1] In the above formula 1, Si P(t(x)) is the silicon concentration (mass ppm) in the produced oil after the reaction t x days, Si F(t(x)) is the silicon concentration (mass ppm) in the feedstock oil after the reaction t x days, LHSV(t(x)) is the liquid space velocity (h - 1) after the reaction t x days, T(t(x)) is the reaction temperature (K) after the reaction t x days, n is the reaction order of the silicon compound adsorption reaction of the catalyst, Ea is the activation energy (J・mol⁻¹) of the silicon compound adsorption reaction of the catalyst, A is the frequency factor of the silicon compound adsorption reaction of the catalyst, R is the gas constant (J・mol⁻¹・K⁻¹), and Si PB is the silicon concentration (mass ppm) in the produced oil under standardized conditions, Si FB is the silicon concentration (mass ppm) in the feedstock oil under standardized conditions, LHSV B is the liquid space velocity (h - 1) under standardized conditions, T B is the reaction temperature (K) under standardized conditions, (t x - t x - 1) ≤ 30 days, and θ (t(x - 1)) is the silicon coating rate of the catalyst after t x - 1 days of the reaction, which is calculated by the following equation 2. [Math 2] In the above formula 2, C Si(t(x-1)) is the amount of silicon deposited per gram of the catalyst after the reaction has elapsed t x-1 days (g), and C Si∞ is the maximum amount of silicon deposited per gram of the catalyst (g).
2. Regarding a hydrogenation reaction carried out by passing feedstock oil containing coker-cracked naphtha containing silicon compounds and hydrogen through a fixed-bed flow reactor packed with a catalyst, Information 1 regarding the reaction rate of the silicon compound adsorption reaction of the catalyst, and an arbitrary reaction t ｘ Information 2 regarding the feedstock oil and information 3 regarding the operating conditions as the days elapse, and the reaction t ｘ Another arbitrary reaction t prior to the time elapsed t ｘ－１ An acquisition unit that acquires information 4 regarding the silicon coating rate of the catalyst after several days, Based on the information 1, information 2, information 3, and information 4 acquired by the acquisition unit, the reaction t ｘ A silicon concentration calculation device comprising a calculation unit that calculates information regarding the silicon concentration in the generated oil discharged from the reactor outlet over time, The information 1 is the reaction order of the silicon compound adsorption reaction of the catalyst, the activation energy of the silicon compound adsorption reaction of the catalyst, and the frequency factor of the silicon compound adsorption reaction of the catalyst. The information 2 above is the silicon concentration in the raw material oil after the reaction t has elapsed for x days. The information 3 is the liquid space velocity at the time t x days have elapsed since the reaction, and the reaction temperature at the time t x days have elapsed since the reaction. The information 4 above is the silicon coating rate of the catalyst after reaction t x-1 days have elapsed. Information regarding the silicon concentration in the generated oil is the silicon concentration in the generated oil after reaction t x days have elapsed. The calculation unit is a silicon concentration calculation device that calculates information regarding the silicon concentration in the generated oil based on the following formula 3. [Math 3] In the above formula 3, Si P(t(x)) is the silicon concentration (mass ppm) in the produced oil after the reaction t x days have elapsed, Si F(t(x)) is the silicon concentration (mass ppm) in the feedstock oil after the reaction t x days have elapsed, LHSV(t(x)) is the liquid space velocity (h - 1) after the reaction t x days have elapsed, T(t(x)) is the reaction temperature (K) after the reaction t x days have elapsed, n is the reaction order of the silicon compound adsorption reaction of the catalyst, Ea is the activation energy (J・mol⁻¹) of the silicon compound adsorption reaction of the catalyst, A is the frequency factor of the silicon compound adsorption reaction of the catalyst, R is the gas constant (J・mol⁻¹・K⁻¹), and Si PB is the silicon concentration (mass ppm) in the produced oil under standardized conditions, Si FB is the silicon concentration (mass ppm) in the feedstock oil under standardized conditions, LHSV B is the liquid space velocity (h - 1) under standardized conditions, T B is the reaction temperature (K) under standardized conditions, (t x - t x - 1) ≤ 30 days, and θ (t(x - 1)) is the silicon coating rate of the catalyst after t x - 1 days of the reaction, which is calculated by the following formula 4. [Math 4] In the above formula 4, C Si(t(x-1)) is the amount of silicon deposited per gram of the catalyst after the reaction has elapsed t x-1 days (g), and C Si∞ is the maximum amount of silicon deposited per gram of the catalyst (g).
3. A silicon concentration calculation program for causing a computer to function as a silicon concentration calculation device according to claim 2.
4. A non-temporary readable recording medium for a computer storing the program described in claim 3.