WO2000077127A1 - Systeme de traitement par purification, dispositif d'analyse de ce traitement, methode analytique associee et support d'enregistrement lisible par ordinateur destine a un programme permettant l'analyse du traitement par purification - Google Patents

Systeme de traitement par purification, dispositif d'analyse de ce traitement, methode analytique associee et support d'enregistrement lisible par ordinateur destine a un programme permettant l'analyse du traitement par purification Download PDF

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Publication number
WO2000077127A1
WO2000077127A1 PCT/JP2000/003751 JP0003751W WO0077127A1 WO 2000077127 A1 WO2000077127 A1 WO 2000077127A1 JP 0003751 W JP0003751 W JP 0003751W WO 0077127 A1 WO0077127 A1 WO 0077127A1
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Prior art keywords
catalyst
refining
reaction
self
purification
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PCT/JP2000/003751
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English (en)
Japanese (ja)
Inventor
Yuichi Takahashi
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Japan Energy Corporation
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Priority to JP2001503968A priority Critical patent/JP3931083B2/ja
Publication of WO2000077127A1 publication Critical patent/WO2000077127A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/72—Controlling or regulating

Definitions

  • the present invention provides a refining treatment system, a refining treatment analyzing apparatus, a refining treatment angle analyzing method, and a refining treatment analyzing device for performing a hydrorefining treatment by bringing a raw oil such as a hydrocarbon oil into contact with a catalyst in a hydrogen atmosphere.
  • the present invention relates to a computer-readable recording medium storing an analysis program.
  • hydrocarbon feedstocks represented by petroleum contain impurities such as sulfur, nitrogen, and metals, and these impurities pose environmental problems when the feedstock is used. It causes various problems such as a title. For this reason, work is usually performed to refine the feedstock oil to remove impurities to a level that can be used.
  • Several methods have been proposed and used in the refining process to remove impurities from the feedstock, but by contacting the feedstock with a catalyst in a hydrogen atmosphere, the sulfur content and nitrogen in the feedstock can be reduced. Hydrogenation is most commonly used to hydrogenate impurities such as hydrogen and sulfur and remove them from the feedstock as hydrogen sulfide, ammonia, and metals.
  • a hydrorefining-type refining apparatus generally has a structure as shown in Fig. 17, in which a feed oil and hydrogen (H 2 ) gas are introduced into reaction towers 2a and 2b filled with a catalyst. Then, the catalyst layers 3 a, 3 b, 3 c, 3 d, 3 e, 3 f and the hydrogen quenching layers 4 a, 4 b, 4 c, 4 d in the reaction towers 2 a, 2 b are made Hydrorefining of the feedstock is performed, and the refined feedstock (refined oil) is recovered.
  • the hornworm medium is made of Mo, Ni, called hydrogenation activity ⁇ ! On an inorganic porous carrier such as alumina, silica alumina, or zeolite.
  • the refined oil can be fractionated into several components using the fractionation device 5 depending on the difference in boiling point and the like.
  • the feedstock was brought into contact with the catalyst under a hydrogen atmosphere.
  • impurities such as sulfur and nitrogen could be removed, but also hydrocarbons contained in the feedstock could be removed. It can be decomposed and isomerized.
  • the term “purification treatment” in this document is intended to include such a treatment for the purpose of decomposition and isomerization in addition to removal of impurities.
  • an effective refining treatment of a feedstock oil is realized by positively utilizing a catalyst.
  • 5,341,313 discloses a hydrodesulfurization simulation, but the catalyst degradation is determined experimentally by a factor of one. For this reason, the catalyst life cannot be predicted with high accuracy when the operating conditions change.
  • Japanese Patent Publication No. 7-1088372 considers the life degradation of the catalyst in the reformer simulator. However, this simulator is for the training of the operator, and does not predict the actual operation state of the equipment. Further, these documents do not consider the deterioration of the hornworm medium due to the accumulation of carbonaceous material and metal in the catalyst pores in the hydrorefining reaction as in the present invention. As described above, there has been no technology to predict the degradation phenomenon of the hornworm medium in detail and accurately, and to optimize the purification conditions by focusing on the degradation phenomenon of the catalyst.
  • the conventional refining process could not sufficiently reduce the cost of the refining process in terms of efficient use of the catalyst.
  • the characteristics of refined oils vary greatly depending on the refining conditions, so in order to obtain refined oils having desired characteristics, it is necessary to perform refining treatment under the most appropriate refining conditions for the characteristics.
  • the extraction of optimal purification conditions relies on the intuition and experience of a technician, which also leads to a rise in costs required for refinement. ing.
  • the present invention has been made in view of such technical problems, and a first object of the present invention is to provide a purification processing system that realizes efficient purification processing and greatly reduces costs required for the purification processing.
  • a second object of the present invention is to provide a refining machine for predicting the product properties of refined oil refined under predetermined conditions and finding out the optimal refining conditions.
  • a third object of the present invention is to accurately predict the product properties of refined oil refined under predetermined conditions in consideration of catalyst deterioration, thereby realizing an efficient purification process. The purpose of this analysis is to provide an analysis method that can be used.
  • a fourth object of the present invention is to provide a computer-readable recording medium storing a refining program for realizing an efficient refining process and greatly reducing the cost required for the refining process. It is in. Disclosure of the invention
  • a refining device for performing a refining treatment by bringing a feedstock into contact with a catalyst under a hydrogen atmosphere;
  • a purification process control device that determines a change in the viability of the self-promoting catalyst with the refinement and controls the purification device based on the determined change in the catalyst activity.
  • a purification processing system is provided. As a result, an efficient purification process can be realized, and the cost required for the purification process can be significantly reduced. Further, according to a second aspect of the present invention, there is provided a refining process analyzer for analyzing a refining process in which a feedstock is brought into contact with a catalyst in a hydrogen atmosphere,
  • a coagulation splitting unit for dividing the self-feeding oil into at least two coagulations
  • the refining process unit which has a refining process result predicting unit that predicts the change of the pseudo component during refining process and the refining process result of lignite oil, Is done.
  • efficient refining can be realized and the cost required for refining can be greatly reduced.
  • a refining method including a change in the il-self-simulating component accompanying the refining process and a refining process result prediction step for predicting the refining process result of the feedstock oil is performed.
  • efficient purification can be realized, and the cost required for purification processing can be significantly reduced.
  • a fourth feature of the present invention is a solution of a refining treatment in which a feedstock is brought into contact with a catalyst under a hydrogen atmosphere.
  • a refining method including a refining process prediction step for predicting the change of the self-simulating component associated with the refining process and the refining process result of the till self-feeding oil is used. Is done.
  • the “recording medium” means a computer-readable medium capable of recording a program, such as a semiconductor memory, a magnetic disk, an optical disk, a magneto-optical disk, a magnetic tape, a digital video disk, IC cards and the like.
  • the catalyst degradation derivation device is a metal that calculates the amount of metal deposited on the self-catalyst during the purification process.
  • the refined oil obtained by the refinement evaluation may be repeatedly subjected to the refinery analysis using the refined oil as a raw material oil. This makes it possible to reduce the change in the catalyst's S 'production in the feed oil flow direction. Can be evaluated. In this case, it is recommended that the intermediate pseudo component is not included as a simulated component during the first refining process, but is included as a translation component in the next and subsequent refining processes. Thereby, the analysis accuracy of the carbon mass deposited on the catalyst is improved.
  • the reaction in which one pseudo component of the feedstock simplifies the other process and the reaction temperature are caused by the heat of reaction and the phase change of the pseudocomponent. It is desirable to consider a mechanism determined in consideration of the amount of heat absorption and heat generation. As a result, the analysis accuracy of the reaction temperature in the purification treatment is improved, and the change in the activity of the catalyst can be more accurately evaluated.
  • FIG. 1 is a block diagram showing a configuration of a purification processing system according to an embodiment of the present invention.
  • FIG. 2 is a flowchart showing a purification treatment method according to the embodiment of the present invention.
  • FIG. 3 is a flowchart showing a purification treatment method according to the embodiment of the present invention.
  • FIGS. 4A and 4B are diagrams respectively showing input data and output data used for the purification process according to the embodiment of the present invention.
  • FIG. 5 is a diagram for explaining a pseudo component dividing method in the purification process according to the embodiment of the present invention, and shows the distribution of carbon number components.
  • FIG. 6 is a diagram for explaining a method for analyzing the distribution of impurities in the catalyst pores in the purification process according to the embodiment of the present invention.
  • Fig. 7 is a graph showing the relationship between the amount of metal deposition experimentally determined and the solvent activity.
  • FIG. 8 is a graph showing the relationship between the amount of carbonaceous deposit and the activity of the solvent obtained experimentally.
  • FIG. 9 is a graph comparing the temperature distribution in the tower output from the purification processing analyzer according to the present invention with the actually measured values.
  • FIG. 10 is a graph comparing the metal deposition amount output from the refining, analysis method and apparatus according to the present invention with the actual measurement.
  • FIG. 11 shows each reaction output from the purification method and apparatus according to the present invention.
  • ⁇ It is a graph showing the amount of carbonaceous deposition.
  • FIG. 12 is a graph comparing the carbonaceous deposition amount output from the purification method and apparatus according to the present invention with the actually measured value.
  • Figure 13 shows the distillation properties of the refined oil (solid line) and the distillation properties of the refined oil actually refined by the refining device (dashed line) obtained from the change in the concentration of each carbon number component obtained in step S105.
  • Fig. 14 shows the inside of a tower operated using two types of feedstocks while adjusting the operation ⁇ J so that the sulfur content of the refined oil could achieve the specified standards for each feedstock. The changes over time of the measured temperature ( ⁇ ) and the analytical value (+) are shown.
  • Figure 15 shows the measured value ( ⁇ ) and the analyzed value (+) of the temporal change in hydrogen consumption.
  • FIG. 16 is a diagram showing an overview of a purification / analysis apparatus according to the embodiment of the present invention.
  • FIG. 17 is a schematic diagram showing a configuration of a purification device.
  • Figure 18 is a conceptual diagram illustrating the mechanism of carbonaceous production.
  • FIG. 19 is a graph showing the relationship between the boiling point obtained by distilling a feedstock oil sample and the amount of distillation components.
  • FIG. 20 is a graph showing the relationship between the boiling point and the carbon number of the distillation component.
  • the refining treatment system 100 includes a refining treatment for removing impurities from the feed oil by bringing the feed oil into contact with the catalyst layer 111 in a hydrogen atmosphere.
  • the refined i ⁇ aa ⁇ analyzer 1 2o is a catalyst degradation analysis (derivation) unit that analyzes changes in the activity of mm 11 due to refining treatment.
  • Using the analysis results of the pseudo component splitting unit 1 2 2 and the catalyst degradation analysis device 1 2 predict the change due to the refining process of each pseudo component and the change in the characteristic of the raw material oil processed by Blue Refining process prediction unit 123, and refining process condition determination to determine the optimal refining conditions for the refining process to obtain a refined oil with desired characteristics set in advance based on the prediction results of the refining process prediction unit 123 Unit 124, Purification parameter control unit 125, which controls the purification parameters of purification device 110 based on the purification conditions output from purification processing condition determination unit 124, Storage for storing input / output data I / O data in storage device 126 based on instructions from device 126, input device 130 The data processing unit 1 2 7 to be converted to the desired de one data format, Interview one Zaintaf
  • the catalyst degradation analyzer 1 2 1 includes a metal deposition amount calculation unit 1 2 a for calculating the amount of metal deposition on the catalyst layer 1 1 1, and a carbon deposition amount for calculating the carbon deposition amount on the catalyst layer 1 1 1.
  • the metal in the catalyst layer 1 1 1 Extracts the activity of the catalyst layer 1 1 1 based on the output tff from the impurity distribution calculator 1 2 1 c and the impurity distribution calculator 1 2 1 c that derives the deposition distribution of impurities such as carbonaceous material. It has an operation unit 1 2 1 d.
  • the refinement device 120 rains the temperature change calculation section 1229 for estimating the change of the catalyst layer.
  • the catalyst data includes the type, amount, and packing state of the catalyst to be packed in the reaction tower used for the purification treatment.
  • the operating data is based on the operating conditions of the reactor, including the amount of feedstock, hydrogen pressure in the reactor, amount of hydrogen, hydrogen purity, fractionation conditions, reactor cross-sectional area, operating target (sulfur content of treated oil / cracking rate) / Temperature).
  • the raw material properties are properties of the raw material oil to be refined, such as distillation properties, sulfur 'nitrogen', residual carbon 'metal (Ni, V) content, bromine value, cracked oil ratio, CP / CN / CA Including.
  • the terms C P, C N, and C A indicate the contents of paraffin (chain lunar aliphatic) hydrocarbons, naphthene (ring lumber) hydrocarbons, and aloma (aromatic) hydrocarbons, respectively.
  • the raw material property data may be obtained by conducting a chemical analysis of the raw oil in advance, or a known data table corresponding to the type of the raw oil is prepared, and the corresponding data is extracted from the data table. You can do it.
  • the feedstock is split into at least two pseudo components based on the input data.
  • the division of recognition can be executed by the following processing. Distill the sample of the feedstock oil to determine the amount of distillation components according to the distillation temperature (boiling point). As shown in Fig. 19, the relationship between the amount of distillation components and the boiling point is determined. On the other hand, the relationship between the boiling point and the carbon number of the component distilled at the boiling point is known from known data as shown in FIG. Therefore, from the relationship between Fig. 19 and Fig. 20, the relationship between the carbon number component (split pseudo-iiM ⁇ ) contained in the feedstock and the content of that component becomes clear. This relationship is shown in Fig. 52. From (5) in Fig.
  • the feedstock oil is composed of components divided (classified) according to the number of carbon atoms.
  • the feedstock is divided into multiple components according to the number of carbon atoms. This is because, as will be described later, each component has a different rate of reaction such as desulfurization and demetallization, and the amount of carbonaceous and metal deposited on the catalyst accompanying the reaction.
  • the carbon components to be split may be split into carbon components with one carbon each over 1 to 60 carbons, or carbons with 2 to 5 carbons. It may be divided for each range of numbers.
  • the feedstock is divided into the components contained in the feedstock as described above, and the catalytic reaction and the resulting carbonaceous and ⁇ !
  • Fig. 5 shows the distribution when another feedstock is divided into carbon components and paraffin / naphthene / aloma.
  • each feedstock is divided into carbon number and paraffin / naphthene / aloma to obtain the distribution,
  • the total abundance of each carbon number component in all the feedstocks supplied to the reaction tower can be determined.
  • each carbon number component has information on impurities such as sulfur, nitrogen, metal (N i, V), residual carbon, and refining, in addition to the ratios of r, raffin / naphthene / aloma. It is desirable.
  • the aroma components are divided into, for example, two types of monocyclic aromatic compounds and polycyclic aromatic compounds. It may be divided. Halo-aromatization ⁇ ) and Since polymorphic aromatic compounds have different reactivities, high-precision analysis can be performed by individually examining a purification reaction model and a catalyst deterioration model described later. Furthermore, in order to make the analysis results more accurate, the aroma may be divided into three or more aromas and the reaction model and the deterioration model may be examined.
  • step S103a assuming that the metal formed by the demetallization reaction (two types of denitration and denitration) of each pseudo component that proceeds with contact with the catalyst accumulates on the catalyst, Obtain the metal deposition amount.
  • the amount of metal deposition per unit time can be calculated by calculating ⁇ C i (in the case of ⁇ ⁇ , and VV) in equation (3) described below. Details of the calculation method will be described later.
  • step S103b the decomposition reaction of each of the components, which proceeds with the contact with the catalyst, the naphthene ring-opening reaction, the aromatization reaction of naphthene, the dearomatization reaction, the degeneration refining reaction, the decarbonization reaction, and the desulfurization reaction
  • the mass of carbon generated is determined.
  • the carbon mass per unit time generated in the desulfurization reaction ⁇ ⁇ ⁇ ;, DS (C20) can be calculated using the following equation.
  • DA DS is a weighting factor related to the probability of occurrence of the desulfurization reaction.
  • T DS is the amount of reaction progress, and is calculated as AC DS in equation (3) described below.
  • E c . ke is the activation energy for carbonaceous production.
  • T is the temperature in the reaction column, and PH2 is the hydrogen partial pressure.
  • FPH 2 is a regulator for the hydrogen partial pressure, and R is the gas constant.
  • This equation is calculated not only for the carbon number component having 20 carbon atoms (C 20) but also for each carbon number component (Cn). Also, for the above reactions other than the deoxidation, the carbonaceous deposition amount can be calculated for each carbon component using an equation using the same parameters as in equation (1).
  • Equation (1) is based on the following assumptions. To date, although some models have been proposed for the mechanism of carbonaceous (also called coke) production, the details have not been fully elucidated. Therefore, in the above equation, it is assumed that there are two routes shown in FIG. 18 in the structure of the click, and the click is performed by these two mechanisms.
  • Step S 103 using the metal deposition amount M i (C n) determined for each carbon number component and the carbonaceous deposition amount AC C. (Cn) determined for each carbon number component for each reaction, Find out how much impurities (metals and carbonaceous materials) are deposited. Specifically, the diffusion equation considering the diffusion of the feedstock oil in the catalyst pores, the surface area of the catalyst, and the deposition reaction was calculated, and the deposition height of the impurities at the depth position in the catalyst pores (unchanged). Object distribution). As shown in FIG. 6, it is assumed that when the feed oil enters the catalyst pores having the pore diameter R, the carbonaceous material 51 and the metal component 52 are deposited on the inner wall of the pores. Carbonaceous 5
  • Equation (2) KMetal , c . ke represents the deposition ⁇ ⁇ constant, r represents the radius of the pore after the impurity has been deposited at the depth position in the pore, and C represents the concentration of the metal or carbonaceous material. Equation (2) is solved by numerical calculation with boundary conditions set using the pore depth h and the diameter R before use, and the deposition height r at the pore depth position is calculated for carbonaceous and metallic materials. Ask for it.
  • step S103d the remaining production of each catalyst layer and catalyst is determined for each reaction based on the impurity distribution of the catalyst.
  • the relationship between the decrease in the catalytic activity of each reaction with the increase in the metal deposition amount and the carbonaceous deposition amount, that is, the change in the insecticidal activity is empirically determined.
  • the graphs in FIGS. 7 and 8 show the change in the phase activity in the desulfurization reaction in response to the change in the amount of metal deposition and the change in the phase shift in the desulfurization reaction in response to the change in the amount of carbonaceous deposition, respectively. .
  • the solid line is a curve approximating the measured value.
  • the degree of decrease in catalytic activity (catalyst degradation) during demolition can be determined from the amount of metal or carbonaceous material deposited.
  • the relationship between the amount of deposited metal and carbonaceous material and the generation of parasites as shown in the graphs of Figs. 7 and 8 was experimentally determined, and the above was determined in step 103c.
  • the change in the activity of the solvent can be determined from the deposited metal amount and the carbonaceous deposited amount. Then, the remaining activity a (i) of the catalyst is determined for each reaction (i).
  • i represents a reaction identification number for a decomposition reaction, a naphthene ring-opening reaction, an aromatization reaction of naphthene, a dearomatization reaction, a delegated refin reaction, a decarbonization reaction, a desulfurization reaction, a demetalization reaction, and a denitrification reaction.
  • the concentration of the substance to be refined from the feed oil as the refining reaction proceeds is determined for each of the fractions, taking into account the remaining activity of the catalyst.
  • the refining reaction includes the desulfurization reaction, denitrification reaction, delegation refin reaction, dearomatization reaction, naphthene opening reaction, decomposition reaction, naphthene aguchi mairida reaction, decarbonization reaction, Ni And demetalization reactions of V
  • the change in the concentration of the purified substance is determined by calculating each reaction formula in consideration of the hydrogen partial pressure dependence, carbon number dependence, and molecular type dependence of the reaction, and the purification process is evaluated. Specifically, for example, the concentration change of the purified substance can be obtained by solving the following reaction equation (3).
  • Equation (3) ai xKo i xCi xexp (—E i / RT) / SV is a factor involved in the reaction, ai is the remaining catalytically active factor, K oi is the reaction constant, C i is the reactant concentration, and E i : Activation energy, T: 3 ⁇ 4J, R: gas constant, SV: liquid space 3 ⁇ 4J.
  • X fi (Other) is a factor for each reaction species, desulfurization, denitrification, derefin, dearomatization (hydrogenated aromatic ring), naphthene ring opening , Cracking, decarbonization, and N and V de- ⁇ ! Reactions, the hydrogen partial pressure dependence fi (P H2 ), carbon number dependence fi (C n), molecular structure (mainly P / N / A) Dependency fi (Structure) and other factors fi (Other) are considered.
  • FCONTx FSIZE X FREGEN X FLOAD is a factor related to the catalyst.
  • FC0NT Influence of catalyst contact efficiency
  • FSIZE Influence of catalyst diameter
  • FREGEN New catalyst / reinfestation media distinction term
  • FL0AD Filling state of catalyst .
  • equation (3) is calculated for each carbon component, and the concentration change of each carbon component is calculated.
  • ⁇ i can be calculated. In this way, it can be seen how the concentrations of all the carbon number components (pseudo-split components) change through each reaction.
  • the amount of metal deposition can be determined as follows, using reaction i in equation (3) as a demetalization reaction.
  • Equation (3) By calculating Equation (3) using 1 and C i as the metal concentration of the feed oil, the demetalized amount AC (de-N i or de-V) in the refined oil is obtained.
  • This demetallization amount AC is the amount of metal deposition in the sword period (for example, on the first day of refining).
  • ⁇ ⁇ accumulation amount By applying this ⁇ ⁇ accumulation amount to the relationship between the relative catalytic activity and the ⁇ S accumulation amount shown in Fig. 7, the insecticidal activity is obtained.
  • the calculated solvent activity corresponds to the coefficient a in equation (3).
  • ⁇ S obtained in the purification process evaluation step (S104) is stored as output data.
  • the output data includes catalyst-related data (metal (Ni, V) deposition data, carbonaceous deposition data, remaining catalyst activity data, etc.) and operation-related data ( ⁇ Behavior (catalyst deterioration degree, inside reaction column), desulfurization rate, denitrification rate, decomposition rate, dearomatic rate, hydrogen consumption, reaction constant, etc.), product data (production volume, specific gravity, sulfur, nitrogen, distillation) Properties, CP / CN / CA, residual coal, etc.).
  • the concentration of each carbon component (i and other components) after purification and sulfur Content, ⁇ content, etc. are obtained. That is, the components and concentrations of the refined oil refined from the reaction tower are predicted.
  • step S106 it is checked whether the special order of the refined oil output in step S105 has reached the expected refining level, and if it has not reached the expected refining level, the input conditions are changed. Then repeat the above calculation until you reach the expected level. Then, when the expected purification level is obtained, the purification conditions (purification parameters) are determined as optimal conditions and stored in the storage device (126).
  • the purification process is performed in the reaction tower using the determined refining conditions (input operation time).
  • the purification process can be performed efficiently, and the cost required for purification can be significantly reduced.
  • one touch obtained by the purification analysis up to step S104! The refined oil may be used as a feed oil for the next catalyst, and the above-mentioned refinement may be repeated. This may result in the case where many types of catalysts are used or the purification conditions change in the reaction tower.
  • the analysis of the purification process can be performed.
  • the reaction formula for determining the change in the concentration of the purified substance includes a reaction in which one pseudo component of the feedstock oil ⁇ ⁇ ⁇ another pseudo component, and the reaction temperature ⁇ changes not only in the heat of reaction but also in the phase change of the pseudo component. It is desirable to include a mechanism that is determined in consideration of the accompanying amount of heat absorption and heat generation.
  • the reaction can be accurately evaluated, and the evaluation accuracy of catalyst deterioration can be improved.
  • the following describes a ⁇ J analysis model that takes into account the fact that when the components of the sword and the like react in the catalyst layer, the generated reaction product generates heat or absorbs heat due to vaporization or liquefaction.
  • the reaction tower for example, as shown in FIG. 17, a plurality of catalyst layers 3a to 3f are provided, and the feedstock oil is purified in each catalyst layer. At this time, each carbon component generates heat or absorbs heat in the catalyst layer due to various chemical reactions.
  • the heat of reaction but also the gas-liquid equilibrium of the substances generated by the reaction are taken into account.
  • a product in which each carbon component is produced by various reactions in each catalyst layer may be gasified (or liquefied) depending on the pressure and temperature conditions in the catalyst layer.
  • the heat of vaporization (heat of liquefaction) is generated by the phase change of these products into a gas phase or a liquid phase, which changes the temperature of the catalyst layer. Therefore, in the present invention, ⁇ of each contact is estimated in consideration of the heat of liquefaction (heat of liquefaction) based on the gas-liquid equilibrium of the reaction product.
  • ⁇ can be expressed as follows.
  • ⁇ is a temperature change due to an external factor unrelated to the catalytic reaction, for example, a change in the contact which decreases due to the introduction of quenching hydrogen.
  • .DELTA..eta kappa heating value in jf himself each reaction H v is the heat of vaporization (liquefaction heat) when the reaction products each carbon number component is generated by the reaction is vaporization (or liquefied).
  • CP is the heat capacity of each carbon component.
  • the second term on the right-hand side of the equation (5) indicates that, in a certain catalyst layer, the reaction heat generated by the reaction i of each carbon number component and the vaporization generated by the reaction product liquefied (or liquefied).
  • the refining paste analyzing apparatus 120 has, for example, an appearance as shown in FIG. That is, the purification processing analyzer 120 according to the embodiment of the present invention is configured by incorporating each element of the purification processing analyzer 120 in the computer system 140.
  • the computer system 140 includes a floppy disk drive 144 and an optical disk drive 144.
  • the refining processing program stored in the medium can be installed in the computer system 140.
  • an appropriate drive device for example, a ROM 144 serving as a memory device and a power cartridge 144 serving as a magnetic tape device can be connected. It can also be used to run an installation of a hydrocarbon oil refinery angular analysis program.
  • the purifying / processing apparatus 120 may be programmed and stored in a computer-readable recording medium.
  • the recording medium may include, for example, a computer-readable medium capable of recording a program such as a semiconductor memory, a magnetic disk, an optical disk, a magneto-optical disk, a magnetic tape, and a digital video disk.
  • the refining analyzer of the present invention can also function as a refining control device for controlling the refining device in connection with the refining device as shown in FIG. Experimental example
  • a hydrotreating apparatus in which a catalyst was filled in a reaction tower was used.
  • This catalyst is divided into 60 layers and displayed for analysis.
  • the first to nine catalyst layers are catalyst layers filled with a demetallation catalyst having a low desulfurization activity.
  • the 10 to 20 layers, 21 to 30 layers, 31 to 40 layers, 41 to 50 layers, and 51 to 60 layers are filled with a desulfurized insect medium having high desulfurization activity.
  • this refining unit is equipped with hydrogen (quenching hydrogen) between the 20 and 21 layers, the 30 and 31 layers, the 40 and 41 layers, the 50 and 51 layers, and the 60 and 61 layers. Built to cool the oil.
  • the temperature of each catalyst layer was estimated according to the Iil self-temperature analysis model.
  • the data of the catalyst charged into the model device was used as the catalyst data in the input data shown in FIG. 4 (a).
  • the operation data is as follows. 3 ⁇ 4 ⁇
  • the gas oil fraction is used as the feed oil, hydrogen pressure: about 8 MPa, liquid space ⁇ : about 2 hr, reaction temperature: 320 to 420 ° C.
  • This feedstock was subjected to a distillation experiment and, according to the results, divided into about 50 categories as described in step S102 above.
  • this split carbon component is used as a purification reaction as a crushing reaction, a nitrogen reaction, a aging reaction, a dearomatization reaction, a naphthene ring-opening reaction, a decomposition reaction, a decarbonization reaction,
  • the de ⁇ ! Reactions of Ni and V were set to simulate ⁇ at each touch ⁇ ! Fig. 9 shows the results. As shown in Fig. 9, the temperature of the feedstock oil has been rising after passing through the catalyst layer 9 filled with the active insect medium, and then temporarily decreased with the introduction of cooling hydrogen. You can see that it is.
  • the metal (N i, V) deposition amount of each layer in the above-described 60-layer purification device was determined according to step S103a.
  • An example of the calculated values is shown in FIG. In FIG. 10, the amount of metal deposition is shown as a temporal change (+) every month when refining is repeated for 12 months.
  • Fig. 10 shows the measured values (life) of the ⁇ ! Deposition amount after 12 months of operation using the actual refining equipment. From Fig. 10, it can be seen that the calculated value (+) after 12 months and the measured value ( ⁇ ) agree well. This indicates that the model used in the angular analysis in step S103a is appropriate.
  • Fig. 11 shows an example of the analysis results using the analysis model for the amount of carbonaceous deposition used in step 103b.
  • the input data for the catalyst, feedstock, and refining equipment are the same as those used in the refining reaction example.
  • curves 1 to 9 represent the amount of carbonaceous material and the amount of carbonaceous precursor generated in the catalyst layers 1 to 60 by the above-described reaction.
  • a model for generating carbonaceous material at the next touch is analyzed.
  • the amount of generated carbonaceous material is obtained as the sum of the amount generated based on the generation of the carbonaceous precursor and the amount of carbonaceous material generated by a reaction such as a decomposition reaction.
  • the distribution of metal deposits and the distribution of carbonaceous deposits can be easily known from the analysis results of the amounts of metal and carbonaceous deposits, making it easier to determine the degree of deterioration of the catalyst and maximizing the life of the catalyst. It is possible to carry out a purification process that makes the most of the efficiency.
  • FIG. 13 shows the properties of the refined oil obtained from the change in the concentration of each carbon number component obtained in step S105 with a solid line.
  • the vertical axis shows the distilling temperature, and the horizontal axis shows the volume of distilling up to that temperature.
  • the relationship between the carbon number component and the boiling point (distillation temperature) was converted again using FIG. Figure 13 also shows the properties of the feedstock (input data).
  • the measured value of the refined oil actually refined by the refinery is shown by a dashed line in the graph, and completely overlaps with the analysis result (solid line) in step S105.
  • the feedstock is lightened by refining (changes to components with lower boiling points).
  • sulfur and nitrogen are separated from impurity components (sulfur-containing compounds and nitrogen-containing compounds) by a desulfurization reaction and a denitrification reaction of each carbon component, so that the boiling point of the remaining components is lowered, and Since the process of changing to a small number of components is added to the analytical model, the distillation properties of refined oil can be predicted with high accuracy.
  • prediction of the distillation properties of refined oil as shown in Fig. 13 is indispensable for accurately predicting the production amount of kerosene, gas oil, etc. obtained by hydrorefining. is there.
  • Figure 14 shows that the two types of feedstocks were operated alternately and operated while adjusting the operation so that the sulfur content of the refined oil reached the specified standard for each feedstock.
  • the measured values of the temperature inside the tower ( ⁇ ) and the analytical values (+) are shown over time.
  • the temperature in the tower can be determined by setting the inlet of the feed oil ⁇ and repeating the calculation so that the analysis result will have a predetermined sulfur content.
  • Fig. 15 shows the measured values ( ⁇ ) and the straight lines (+) of the change over time in hydrogen consumption using the same feedstock oil used in Fig. 14.
  • Hydrogen consumption is calculated as the total amount of hydrogen consumption and generation based on the change in the concentration of each carbon component obtained by equation (3) due to each reaction.
  • the results agree well for different feedstocks, indicating that the refining models such as desulfurization and denitrification are valid. From this result, it is possible to estimate the operation efficiency of the refiner, etc., and feed this ⁇ g into the actual refiner to judge the change in the number of operating days to perform efficient refinement. it can.
  • the amount of sulfur contained per unit refined oil amount as the number of operating days of the refining process may be simulated may be simulated.
  • the sulfur level which is set in advance, is set in the analyzer, and if the level exceeds the allowable level, ⁇ indicates the number of operating days. Can be managed.
  • the relative activity and the ⁇ ! Alternatively, the experimental relationship between the amounts of carbonaceous materials was used, but it is also possible to calculate the catalyst net activity using the results of the impurity distribution in the pores obtained in step 103c.
  • the catalyst deterioration phenomenon Since the purification can be performed while referring to the relevant information, an efficient purification process can be realized, and the cost required for the purification can be greatly reduced.
  • the temperature change can be predicted with high accuracy in consideration of the gas-liquid equilibrium for each contact, the prediction accuracy of catalyst reaction and catalyst deterioration is improved. This makes it possible to operate the refinery with the optimal purification schedule.
  • the refining device of the present invention it is possible to analyze the refining process while referring to the “iff” related to the deterioration phenomenon of the catalyst, so that efficient refining is realized and the refining process is required. Expenses can be significantly reduced.
  • the catalyst degradation is analyzed separately for a plurality of components constituting the feedstock oil and a plurality of possible reactions. Further, by predicting the change in consideration of the gas-liquid equilibrium for each catalyst layer, more accurate analysis results can be obtained. Further, according to the purification processing method of the present invention, the purification can be analyzed with reference to tffg relating to the catalyst deterioration phenomenon, so that efficient purification can be realized and the cost required for the purification processing can be reduced. It can be greatly reduced. In addition, since the catalyst degradation is analyzed separately for a plurality of components forming the feed oil and a plurality of possible reactions, extremely high-precision analysis results can be obtained.
  • the purification process can be predicted with high accuracy. .
  • the cost required for the hydrocarbon oil refining process can be significantly reduced.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un système de traitement par purification comprenant un dispositif de purification (110) destiné au traitement par purification par le contact d'une huile à base de matières premières avec un catalyseur dans une atmosphère d'hydrogène, et un dispositif permettant d'analyser le traitement par purification (120). Ce dispositif sélectionne le mode de purification souhaité en analysant la modification des caractéristiques d'une matière première associée au traitement par purification, compte tenu de l'évolution de l'activité du catalyseur en fonction du traitement de purification. Ainsi, des dépôts métalliques et carbonés peuvent se former à l'intérieur des pores du catalyseur et le dispositif de purification peut être commandé par le choix du mode de purification. Ce système permet d'obtenir un traitement par purification efficace et de réduire les coûts nécessaires à un tel traitement.
PCT/JP2000/003751 1999-06-11 2000-06-09 Systeme de traitement par purification, dispositif d'analyse de ce traitement, methode analytique associee et support d'enregistrement lisible par ordinateur destine a un programme permettant l'analyse du traitement par purification WO2000077127A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002146363A (ja) * 2000-11-06 2002-05-22 Showa Shell Sekiyu Kk 水素化脱硫触媒の活性低下を予測する方法およびそれを用いた水素化脱硫装置の運転方法
JP2006265126A (ja) * 2005-03-22 2006-10-05 National Institute Of Advanced Industrial & Technology 反応熱の推算方法及び装置
JP2007023000A (ja) * 2005-07-21 2007-02-01 Mitsubishi Chemicals Corp アセチレン水添器の制御方法
WO2018216746A1 (fr) * 2017-05-25 2018-11-29 コスモ石油株式会社 Procédé, serveur, commande lisible par ordinateur et support d'enregistrement permettant de fournir un état de fonctionnement recommandé pour une installation

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US5341313A (en) * 1992-08-03 1994-08-23 Phillips Petroleum Company Catalyst life prediction in hydrodesulfurization
JPH0784606A (ja) * 1993-09-09 1995-03-31 Idemitsu Kosan Co Ltd 多段断熱反応器の最適化制御方法及びその装置
JPH07108372B2 (ja) * 1988-05-11 1995-11-22 横河電機株式会社 触媒反応形リアクターのシミュレータ

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JPH07108372B2 (ja) * 1988-05-11 1995-11-22 横河電機株式会社 触媒反応形リアクターのシミュレータ
US5341313A (en) * 1992-08-03 1994-08-23 Phillips Petroleum Company Catalyst life prediction in hydrodesulfurization
JPH0784606A (ja) * 1993-09-09 1995-03-31 Idemitsu Kosan Co Ltd 多段断熱反応器の最適化制御方法及びその装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002146363A (ja) * 2000-11-06 2002-05-22 Showa Shell Sekiyu Kk 水素化脱硫触媒の活性低下を予測する方法およびそれを用いた水素化脱硫装置の運転方法
JP2006265126A (ja) * 2005-03-22 2006-10-05 National Institute Of Advanced Industrial & Technology 反応熱の推算方法及び装置
JP2007023000A (ja) * 2005-07-21 2007-02-01 Mitsubishi Chemicals Corp アセチレン水添器の制御方法
WO2018216746A1 (fr) * 2017-05-25 2018-11-29 コスモ石油株式会社 Procédé, serveur, commande lisible par ordinateur et support d'enregistrement permettant de fournir un état de fonctionnement recommandé pour une installation
US10915837B2 (en) 2017-05-25 2021-02-09 Cosmo Oil Co., Ltd. Method, server, computer-readable command, and recording medium for providing recommended operation condition for plant

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