CN112530524B - Modeling method for catalytic reforming reaction - Google Patents
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 223
- 238000001833 catalytic reforming Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004939 coking Methods 0.000 claims abstract description 52
- 238000004364 calculation method Methods 0.000 claims abstract description 23
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 32
- 238000006757 chemical reactions by type Methods 0.000 claims description 31
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 29
- 230000000694 effects Effects 0.000 claims description 27
- 239000000571 coke Substances 0.000 claims description 25
- 150000001924 cycloalkanes Chemical class 0.000 claims description 25
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006057 reforming reaction Methods 0.000 claims description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 13
- 238000006900 dealkylation reaction Methods 0.000 claims description 13
- 239000012530 fluid Substances 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 230000009056 active transport Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006317 isomerization reaction Methods 0.000 claims description 10
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 9
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 8
- 238000007363 ring formation reaction Methods 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 239000011800 void material Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000006049 ring expansion reaction Methods 0.000 claims description 5
- 241000282326 Felis catus Species 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 230000000704 physical effect Effects 0.000 claims description 4
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 241001120493 Arene Species 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 16
- 238000005504 petroleum refining Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 10
- 239000003502 gasoline Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 230000020335 dealkylation Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000002407 reforming Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- -1 demethylation Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012773 Laboratory assay Methods 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
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- G—PHYSICS
- G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
- G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
- G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
- G16C20/10—Analysis or design of chemical reactions, syntheses or processes
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of petroleum refining, in particular to a modeling method for catalytic reforming reaction, which comprises the following steps: dividing the reaction mass into 58 lumped components based on lumped theory; combining the division of the lumped components to establish a catalytic reforming reaction network; according to the catalytic reforming reaction network, a catalytic reforming reaction model is established; parameters in the catalytic reforming reaction model are calibrated. The invention has the beneficial effects that: based on 58 lumped components and 301 dynamic equations, a catalytic reforming reaction model is established, and a dynamic modeling mode of hydrogenolysis reaction, polymerization reaction and coking reaction is provided; the calibration process of the dynamic parameters is classified, the original 652 parameters to be calibrated are simplified into tens, the solving difficulty of the model is greatly reduced on the premise of not influencing the model precision, and the calculation speed is improved.
Description
Technical Field
The invention relates to the field of petroleum refining, in particular to a modeling method for catalytic reforming reaction.
Background
Catalytic reforming (Catalytic Reforming) is one of the main processes for petroleum refining. The method is a process for converting naphtha into reformed oil rich in aromatic hydrocarbon and producing hydrogen as a byproduct under the conditions of certain temperature, pressure, hydrogen and the presence of a catalyst. The primary purpose of the catalytic reforming process is to produce high octane gasoline or aromatics. When producing high octane gasoline, the feed is a wide cut, typically with a boiling point range of 80 to 180 ℃ cut. When aromatic hydrocarbons are produced, the feed is a narrow cut, and the boiling point range is typically 60 to 145 ℃ cut or 60 to 165 ℃.
The catalytic reforming reaction part is a core operation unit in the whole process, and the design of the reactor and the selection of the operation conditions directly influence the yield and quality of the product. The main chemical reactions of the catalytic reforming process are: six-membered cycloalkane dehydrogenation, five-membered cycloalkane isomerization dehydrogenation, alkane dehydrogenation cyclization, straight-chain alkane isomerization, hydrogenolysis and hydrocracking of hydrocarbons, demethylation, arene dealkylation, carbon deposition reaction and the like. The catalytic reforming reaction components which can be analyzed by the gas chromatograph are more than 300, and the coupling among the components is strong, so that the whole reaction system is combined into a complex reaction network by a plurality of parallel, serial, reversible, irreversible and other reactions. Therefore, the catalytic reforming reaction belongs to a complex reaction system.
Since the 50 s of the 20 th century, catalytic reforming reaction models constructed based on lumped theory have been widely used, and after the requirements of comprehensive trade-off research and industrial application of various large petroleum companies and scientific research institutions, various catalytic reforming lumped reaction kinetic models are developed, and the lumped quantity is developed from 4 lumped in the early stage to 38 lumped 86 reactions. These lumped reaction kinetic models can be used to describe overall conversion, product yield, thermal efficiency of the process, etc., and can also be used to predict product quality, seek optimal production and operating conditions, etc.
The division of the lumped components of most of the existing models leads to poor universality of the models, and in addition, the parameter calibration method is not reasonable, so that the calibration process is difficult to solve or the solving time is long.
Disclosure of Invention
In order to solve the problems, the invention provides a modeling method for catalytic reforming reaction.
A catalytic reforming reaction modeling method, comprising:
dividing the reaction mass into 58 lumped components based on lumped theory;
combining the division of the lumped components to establish a catalytic reforming reaction network;
according to the catalytic reforming reaction network, a catalytic reforming reaction model is established;
parameters in the catalytic reforming reaction model are calibrated.
Preferably, the 58 lumped components include:
alkane: 27, from C1 to C14, C12, C13, C14 do not distinguish normal and isomerism, C6, C7, C8 alkanes are divided into normal, mono-branched and multi-branched isomerism, C4, C5, C9, C10, C11 are divided into normal and isomerism;
cycloalkane: 16, from C5 to C14, C5 is only five-membered cycloalkane, C6 to C11 are divided into five-membered cycloalkane and six-membered cycloalkane, and C12, C13 and C14 are only expressed by cycloalkanes;
aromatic hydrocarbons: 13, from C6 to C14, C8 aromatics are further divided into ethylbenzene, ortho-xylene, meta-xylene and para-xylene;
and (3) coke: coKE, which means the COKE produced by the coking reaction, adheres to the catalyst;
hydrogen gas: h 2 。
Preferably, the catalytic reforming reaction network comprises 301 kinetic reactions including 9 isomerization reactions, 26 cyclization reactions, 6 ring expansion reactions, 9 dehydrogenation reactions, 59 hydrogenolysis reactions, 35 naphthene dealkylation reactions, 79 hydrocracking reactions, 36 aromatic dealkylation reactions, 6 polymerization reactions, and 36 coking reactions.
Preferably, the establishing a catalytic reforming reaction model includes:
material balance model of the reactor:
energy balance model of the reactor:
wherein u is the reactant flow linear velocity; z is the axial distance of the reactor; c A To the concentration of component A, RATE i The reaction rate of each reaction is the ith reaction; x is X A,i Is the stoichiometric coefficient of component A in each reaction of the ith; ρ is the material density; c (C) P Is specific heat capacity; t is the reaction temperature; ΔH i Is the reaction heat of the ith reaction.
Preferably, the modeling of the catalytic reforming reaction includes
For all reactions except coking reactions, a reaction rate equation was established:
wherein Rate is the reaction Rate; ACT (active transport protocol) global Is a global active factor; ACT (active transport protocol) cat Is the integral active factor of the catalyst; ACT (active transport protocol) site An active factor that is an acidic or metallic site; ACT (active transport protocol) reac Is a reaction type active factor; epsilon is the void ratio of the reactor bed; ρ P Is the catalyst particle density; p is the reaction pressure; p (P) 0 Is the reference pressure; p_exp is the index of the pressure factor phase; [ A ]]、[B]、[C]、[D]Is the partial pressure of the components; a. b, c and d are reaction metering coefficients; the fact is the pressure index of the driving force item; k (K) f Is a positive reaction rate constant; k (K) eq Is a balance constant;
for coking reactions, a reaction rate equation is established:
in the method, in the process of the invention,CnHm is a component capable of undergoing coking reaction and comprises alkane, penta-cycloalkane and arene; COKEACT sys Is an active factor of a reaction system; COKEACT rxi Is a reactor active factor; COKEACT reac The reaction type is active factors of coking reaction type, and the reaction type comprises alkane coking, naphthene coking and aromatic hydrocarbon coking; h2HC is the hydrogen-hydrocarbon ratio in the reactor; h2HC 0 Is a hydrogen-hydrocarbon ratio standard; hc_exp is the index of the hydrogen to hydrocarbon ratio factor term; cxMULT is a coefficient of coking rate of components with different carbon numbers, and the more the carbon number of the components is, the more easily the components are coked; [ CnHm ]]Is the mole fraction of the reactants.
Preferably, the calibrating the parameters in the catalytic reforming reaction model includes:
calibrating the factor before finger:
k 0 ＝k type ×k Ci ×k base ；
k base a pre-finger factor reference value for each reaction; k (k) type Is an adjustment parameter based on the reaction type; k (k) Ci The method is characterized in that the method takes the carbon atom number of a reactant as a reference adjustment parameter, the reactions of the reactant with the same carbon atom number under each reaction type are classified, 1 adjustment parameter is set, and only one adjustment parameter is set for coking reaction;
based on the reaction type, the same reaction type prescribes the same activation energy for calibration of the activation energy;
when the reaction result is greatly different from the actual result and is greatly affected by the reaction balance, the balance constant of the reaction is calibrated.
Preferably, the calibrating the parameters in the catalytic reforming reaction model includes:
global activity in the reforming reaction, each reaction type activity, and catalyst activity were calibrated.
Preferably, the calibrating the parameters in the catalytic reforming reaction model includes:
the partition ratio of each parallel reaction was calibrated.
Preferably, the calibrating the parameters in the catalytic reforming reaction model includes:
the reactor pressure drop was calculated by the Ergun equation:
wherein U is apparent flow rate; epsilon is the bed void fraction; μ is the fluid viscosity; d (D) P Is the diameter of the catalyst particles; phi S Is the spherical factor of the catalyst particles; ρ is the fluid density;
the calculation of the pressure drop of the system is simplified into the correlation between the fluid flow and physical properties, the pressure drop factor is introduced for parameter calibration, and the correlation of the pressure drop of the system is as follows:
ΔP＝MOLF*MASF*MOLV*DPF
wherein MOLF is the molar flow of fluid; MASF is mass flow; MOLV is the molar volume; DPF is a pressure drop factor.
Preferably, the calibrating the parameters in the catalytic reforming reaction model includes:
by establishing a correlation with the reaction temperature, according to the actual product analysis, and calibrating related parameters, the proportion of each component is obtained:
wherein, ISO_PERC is the proportion of isomers; T_AVG is the average temperature of the reactor; A. and B is a parameter, and calibration is carried out according to actual data.
The invention has the beneficial effects that:
1. based on 58 lumped components and 301 catalytic reforming reaction models established by dynamic equations, the applicability and application range of the models are greatly improved;
2. classifying the calibration process of the dynamic parameters, simplifying the original 652 parameters to be calibrated into tens of parameters, greatly reducing the solving difficulty of the model and improving the calculation speed on the premise of not influencing the model precision;
3. the global activity, the activity of each reaction type and the activity of the catalyst in the reforming reaction are calibrated, so that the parameter calibration of the model is more flexible, and the model prediction precision is improved;
4. calibrating the distribution ratio of each parallel reaction, and improving the model prediction precision;
5. the calculation of the pressure drop of the system is simplified into the association between the fluid flow and physical properties, and a pressure drop factor is introduced for parameter calibration, so that the model prediction accuracy is improved;
6. and the proportion of each component is obtained by establishing a correlation with the reaction temperature and calibrating related parameters according to the analysis of actual products, so that the model prediction accuracy is improved.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a schematic illustration of a process flow of a reaction section of a continuous reformer in a refinery;
FIG. 2 is a schematic flow chart of a modeling method of catalytic reforming reaction according to an embodiment of the present invention;
FIG. 3 is a schematic illustration of a process flow of a reforming reaction system model;
fig. 4 is a network diagram of a catalytic reforming reaction in a modeling method of the catalytic reforming reaction according to an embodiment of the present invention.
Detailed Description
The technical scheme of the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to these examples.
FIG. 1 is a schematic illustration of a process flow of a reaction section of a continuous reformer in a refinery. The device specifically comprises a first reactor 1, a second reactor 2, a third reactor 3, a fourth reactor 4, a first heating furnace 5, a second heating furnace 6, a third heating furnace 7, a fourth heating furnace 8, a feeding and discharging heat exchanger 9, an air cooler 10, a pump 11, a product separation tank 12 and a circulating hydrogen compressor 13. The reforming reactor adopts a double-overlapping structure, the internal components of the reactor adopt a centripetal flow type, and the material flow radially passes through the catalyst bed layer and is up-in and down-out (central tube down-flow). The reaction heating furnace adopts a two-in-two box type heating furnace, adopts a multi-flow path U-shaped low pressure drop furnace tube and has low pressure dropNO x A burner. The reformed hydrogen is boosted by a reforming recycle hydrogen compressor and then sent to a re-contact part for further compression.
Based on the above examples, the embodiment of the present invention proposes a modeling method for catalytic reforming reaction, as shown in fig. 2, including the following steps:
s1: based on the lumped theory, the reaction mass was divided into 58 lumped components.
The raw material of the catalytic reforming device is naphtha, the products comprise hydrogen, liquefied gas, reformed gasoline, mixed aromatic hydrocarbon and the like, the components involved are more than 300, and the reforming components are generally integrated into a plurality of virtual components based on a lumped theory during die construction. Along with the continuous development of laboratory assay analysis technology, analysis of the reformed materials in actual production is more and more refined, and lumped components are divided into the whole as much as possible based on the consideration of model generality.
In reforming reaction, there is isomerization reaction of alkane, at the same time, the dehydrocyclization rate of normal and isoparaffin is greatly different, in reforming gasoline, the contribution of normal and isoparaffin to gasoline octane number is also different, so that the alkane is divided into normal and isoparaffin, and the isomerism of important component is divided into single branched chain and multi branched chain. According to the reaction mechanism, alkane dehydrocyclization first generates a five-membered ring, which is isomerized to generate a six-membered ring, thus dividing cycloalkanes into five-membered rings and six-membered rings. Light hydrocarbons are subdivided into C1-C5 alkanes based on hydrocracking and hydrogenolysis reactions, while C4, C5 are further divided into normal, isoparaffins, taking into account the liquefied gas product composition. In view of the aromatics production scheme, the C8 aromatics are divided into ethylbenzene, ortho-xylene, meta-xylene and para-xylene. Generally, the main composition of naphtha is between C6 and C11, and the C12, C13 and C14 components are defined in consideration of the diversity of naphtha sources and the existence of polymerization reactions. The coke composition is defined by the presence of coking reactions.
According to the reaction kinetics characteristics and the actual production device requirements, the 58 lumped components are divided as follows:
alkane: 27, from C1 to C14, C12, C13, C14 do not distinguish normal and isomerism, C6, C7, C8 alkanes are divided into normal, mono-branched and multi-branched isomerism, C4, C5, C9, C10, C11 are divided into normal and isomerism;
cycloalkane: 16, from C5 to C14, C5 is only five-membered cycloalkane, C6 to C11 are divided into five-membered cycloalkane and six-membered cycloalkane, and C12, C13 and C14 are only expressed by cycloalkanes;
aromatic hydrocarbons: 13, from C6 to C14, C8 aromatics are further divided into ethylbenzene, ortho-xylene, meta-xylene and para-xylene;
and (3) coke: coKE, which means the COKE produced by the coking reaction, adheres to the catalyst;
hydrogen gas: h 2 。
In view of the above, the feed composition of the reformer was divided into 58 lumped components as shown in table 1.
TABLE 1 catalytic reforming reaction 58 lumped components
| Number of carbon atoms | Alkanes | Cycloalkane (CNS) | Aromatic hydrocarbons | Hydrogen gas | Coke (coke) |
| 1 | P 1 | ||||
| 2 | P 2 | ||||
| 3 | P 3 | ||||
| 4 | P 4 ,iP 4 ,nP 4 | ||||
| 5 | P 5 ,iP 5 ,nP 5 | 5N 5 | |||
| 6 | nP 6 ,MBP 6 ,SBP 6 | 5N 6 ,6N 6 | A 6 | ||
| 7 | nP 7 ,MBP 7 ,SBP 7 | 5N 7 ,6N 7 | A 7 | ||
| 8 | nP 8 ,MBP 8 ,SBP 8 | 5N 8 ,6N 8 | A 8 ,EB,OX,MX,PX | ||
| 9 | nP 9 ,iP 9 | 5N 9 ,6N 9 | A 9 | ||
| 10 | nP 10 ,iP 10 | 5N 10 ,6N 10 | A 10 | ||
| 11 | nP 11 ,iP 11 | 5N 11 ,6N 11 | A 11 | ||
| 12 | P 12 | N 12 | A 12 | ||
| 13 | P 13 | N 13 | A 13 | ||
| 14 | P 14 | N 14 | A 14 | ||
| H 2 | COKE |
Wherein, P: alkanes, not distinguishing normal from heterogeneous; iP: isoparaffins, without distinguishing the number of branches; and nP: n-alkanes; MBP: a multi-branched isoparaffin; SBP: single branched isoparaffin; 5N: five membered cycloalkanes; 6N: six-membered cycloalkane; n: cycloalkanes, which do not distinguish between the number of carbon atoms on the ring; a: aromatic hydrocarbons; EB: ethylbenzene, OX: ortho-xylene, MX: meta-xylene, PX: para-xylene; h 2 : hydrogen gas; COKE: and (3) coke.
S2: and combining the division of the lumped components to establish a catalytic reforming reaction network.
The catalytic reforming reaction network has 301 kinetic reactions, including 9 isomerization reactions (reversible), 26 cyclization reactions (reversible), 6 ring expansion reactions (reversible), 9 dehydrogenation reactions (reversible), 59 hydrogenolysis reactions, 35 naphthene dealkylation reactions, 79 hydrocracking reactions, 36 arene dealkylation reactions, 6 polymerization reactions and 36 coking reactions. In combination with the partitioning characteristics of the lumped components, a structured reaction network is formed, as shown in fig. 4.
Isomerization reaction:
cyclization reaction:
ring expansion reaction:
dehydrogenation reaction:
hydrogenolysis reaction:
MBP 6 ,SBP 6 ,nP 6 +H 2 →(P 1 +P 5 ),(P 2 +P 4 ),(P 3 +P 3 )
MBP 7 +H 2 →(P 1 +SBP 6 ),(P 2 +P 5 ),(P 3 +P 4 )
SBP 7 ,nP 7 +H 2 →(P 1 +nP 6 ),(P 2 +P 5 ),(P 3 +P 4 )
MPP 8 +H 2 →(P 1 +SBP 7 ),(P 2 +SBP 6 ),(P 3 +P 5 ),(P 4 +P 4 )
SBP 8 ,nP 8 +H 2 →(P 1 +nP 7 ),(P 2 +nP 6 ),(P 3 +P 5 ),(P 4 +P 4 )
iP 9 +H 2 →(P 1 +SBP 8 ),(P 2 +SBP 7 ),(P 3 +SBP 6 ),(P 4 +P 5 )
nP 9 +H 2 →(P 1 +nP 8 ),(P 2 +nP 7 ),(P 3 +nP 6 ),(P 4 +P 5 )
iP 10 +H 2 →(P 1 +iP 9 ),(P 2 +SBP 8 ),(P 3 +SBP 7 ),(P 4 +SBP 6 ),(P 5 +P 5 )
nP 10 +H 2 →(P 1 +nP 9 ),(P 2 +nP 8 ),(P 3 +nP 7 ),(P 4 +nP 6 ),(P 5 +P 5 )
iP 11 +H 2 →(P 1 +iP 10 ),(P 2 +iP 9 ),(P 3 +SBP 8 ),(P 4 +SBP 7 ),(P 5 +SBP 6 )
nP 11 +H 2 →(P 1 +nP 10 ),(P 2 +nP 9 ),(P 3 +nP 8 ),(P 4 +nP 7 ),(P 5 +nP 6 )
naphthene dealkylation:
5N 6 +H 2 →5N 5 +P 1
5N 7 +H 2 →(5N 6 +P 1 ),(5N 5 +P 2 )
6N 7 +H 2 →6N 6 +P 1
5N 8 +H 2 →(5N 7 +P 1 ),(5N 6 +P 2 ),(5N 5 +P 3 )
6N 8 +H 2 →(6N 7 +P 1 ),(6N 6 +P 2 )
5N 9 +H 2 →(5N 8 +P 1 ),(5N 7 +P 2 ),(5N 6 +P 3 ),(5N 5 +P 4 )
6N 9 +H 2 →(6N 8 +P 1 ),(6N 7 +P 2 ),(6N 6 +P 3 )
5N 10 +H 2 →(5N 9 +P 1 ),(5N 8 +P 2 ),(5N 7 +P 3 ),(5N 6 +P 4 ),(5N 5 +P 5 )
6N 10 +H 2 →(6N 9 +P 1 ),(6N 8 +P 2 ),(6N 7 +P 3 ),(6N 6 +P 4 )
5N 11 +H 2 →(5N 10 +P 1 ),(5N N +P 2 ),(5N 8 +P 3 ),(5N 7 +P 4 ),(5N 6 +P 5 ),(5N 5 +SBP 6 )
6N 10 +H 2 →(6N 10 +P 1 ),(6N 9 +P 2 ),(6N 8 +P 3 ),(6N 7 +P 4 ),(6N 6 +P 5 )
hydrocracking reaction:
P 5 +H 2 →(P 1 +P 4 ),(P 2 +P 3 )
MBP 6 ,SBP 6 ,nP 6 +H 2 →(P 1 +P 5 ),(P 2 +P 4 ),(P 3 +P 3 )
MBP 7 +H 2 →(P 1 +SBP 6 ),(P 2 +P 5 ),(P 3 +P 4 )
SBP 7 ,nP 7 +H 2 →(P 1 +nP 6 ),(P 2 +P 5 ),(P 3 +P 4 )
MBP 8 +H 2 →(P 1 +SBP 7 ),(P 2 +SBP 6 ),(P 3 +P 5 ),(P 4 +P 4 )
SBP 8 ,nP 8 +H 2 →(P 1 +nP 7 ),(P 2 +nP 6 ),(P 3 +P 5 ),(P 4 +P 4 )
iP 9 +H 2 →(P 1 +SBP 8 ),(P 2 +SBP 7 ),(P 3 +SBP 6 ),(P 4 +P 5 )
nP 9 +H 2 →(P 1 +nP 8 ),(P 2 +nP 7 ),(P 3 +nP 6 ),(P 4 +P 5 )
iP 10 +H 2 →(P 1 +iP 9 ),(P 2 +SBP 8 ),(P 3 +SBP 7 ),(P 4 +SBP 6 ),(P 5 +P 5 )
nP 10 +H 2 →(P 1 +nP 9 ),(P 2 +nP 8 ),(P 3 +nP 7 ),(P 4 +nP 6 ),(P 5 +P 5 )
iP 11 +H 2 →(P 1 +iP 10 ),(P 2 +iP 9 ),(P 3 +SBP 8 ),(P 4 +SBP 7 ),(P 5 +SBP 6 )
nP 11 +H 2 →(P 1 +nP 10 ),(P 2 +nP 9 ),(P 3 +nP 8 ),(P 4 +nP 7 ),(P 5 +nP 6 )
P 12 +H 2 →(P 1 +iP 11 ),(P 2 +iP 10 ),(P 3 +iP 9 ),(P 4 +SBP 8 ),(P 5 +SBP 7 ),(SBP 6 +SBP 6 )
P 13 +H 2 →(P 1 +P 12 ),(P 2 +iP 11 ),(P 3 +iP 10 ),(P 4 +iP 9 ),(P 5 +SBP 8 ),(SBP 6 +SBP 7 )
P 14 +H 2 →(P 1 +P 13 ),(P 2 +P 12 ),(P 3 +iP 11 ),(P 4 +iP 10 ),(P 5 +iP 9 ),(SBP 6 +SBP 8 ),(SBP 7 +SBP 7 )
dealkylation of aromatic hydrocarbon:
A j +H 2 →(A j-1 +P 1 ),(A j-2 +P 2 ),…,(A 6 +P j-6 ),j＝7～11
A j +H 2 →(A j-1 +P 1 ),(A j-2 +P 2 ),…,(A j-5 +P 5 ),…,(A j-6 +SBP 6 ),…,(A 6 +SBP j-6 ),j＝12,13,14
polymerization reaction:
A 7 +P j →A 7+j +H 2 ,j＝3,4,5
A 9 +P j →A 8+j +H 2 ,j＝2,3,4
coking reaction:
MBP j ,SBP j →COKE+xH 2 ,j＝6,7,8
nP j →COKE+xH 2 ,j＝6～11
iP j →COKE+xH 2 ,j＝9,10,11
P j →COKE+xH 2 ,j＝12,13,14
5N j →COKE+xH 2 ,j＝6～11
N j →COKE+xH 2 ,j＝12,13,14
A j →COKE+xH 2 ,j＝6～14。
s3: and establishing a catalytic reforming reaction model according to the catalytic reforming reaction network.
As shown in fig. 3, the process flow of the reforming reaction system model includes a feed system, a reaction module, a separation circulation system, and a catalyst scorch system.
Wherein the reactor in the reaction module comprises the following calculation model:
material balance model of the reactor:
energy balance model of the reactor:
wherein u is the reactant flow linear velocity; z is the axial distance of the reactor; c A To the concentration of component A, RATE i The reaction rate of each reaction is the ith reaction; x is X A,i Is the stoichiometric coefficient of component A in each reaction of the ith; ρ is the material density; c (C) P Is specific heat capacity; t is the reaction temperature; ΔH i Is the reaction heat of the ith reaction.
In this example, a corresponding reaction rate calculation formula is also presented for the kinetic reaction. The catalytic reforming reaction is treated in a quasi-homogeneous phase, and the kinetic reaction is a simple first-order reaction relative to each component and has an exponential relation with the reaction pressure.
For all reactions except coking reactions, the reaction equation is expressed as:
the reaction rate equation can be expressed as:
wherein Rate is the reaction Rate, kmol/kgcat hr; ACT (active transport protocol) global Is a global active factor, associated with each reaction; ACT (active transport protocol) cat Is a catalyst overall activity factor, and is related to all reactions except coking reactions; ACT (active transport protocol) site Active factors, either acidic or metallic, are involved in the reactions that occur at the corresponding active site; ACT (active transport protocol) reac For reactive species of active factors, each species has a different activityA sex factor; epsilon is the void ratio of the reactor bed; ρp is the catalyst particle density; p is the reaction pressure, kPa; p (P) 0 101.325kPa for a baseline pressure; p_exp is the index of the pressure factor phase, and different reaction types have different indexes; [ A ]]、[B]、[C]、[D]Partial pressure of components, kPa; a. b, c and d are reaction metering coefficients; face is the pressure index of the driving force term, equal to a+b or c+d.
K f For the positive reaction rate constant, it is calculated according to the Arrhenius formula:
K f ＝k 0 ×e -E/RT
wherein k is 0 Is a pre-finger factor; e is activation energy, J/mol; r is an ideal gas constant, 8.314J/(mol.K); t is the reaction temperature, K.
K eq For the equilibrium constant, the correlation with temperature is calculated as follows:
wherein T is the reaction temperature, K; k (K) par As coefficients, adjustable at parameter calibration; A. b, C, D is a constant.
Based on the coking reaction mechanism, coke is formed from polycyclic hydrocarbons, which are formed from alkane cyclization (or isomerization) and intermediate olefins produced from aromatic hydrocarbons. In the actual reaction process, the dehydrogenation rate of the hexacyclic naphthene is extremely high, and almost no conversion into coke is carried out, so that only the coking of the pentacyclic naphthene is considered; after the 2 nd reactor, the content of naphthenes was small, and it was difficult to calculate the reaction rate. Thus, it was determined that most of the coke was produced from the heavy components of C9 and above and was mainly produced in the last reactor. Coking reactions can be classified into 3 categories by reactant: alkane coking reaction, five-membered cycloalkane coking reaction and arene coking reaction.
The reaction equation is expressed as:
C n H m →aCOKE+bH 2
the reaction rate equation is expressed as:
wherein CnHm is a component capable of undergoing coking reaction, and comprises alkane, penta-cycloalkane and arene; COKEACT sys Is an active factor of a reaction system; COKEACT rxi Is a reactor active factor; COKEACT reac The reaction type is active factors of coking reaction type, and the reaction type comprises alkane coking, naphthene coking and aromatic hydrocarbon coking; h2HC is the hydrogen-hydrocarbon ratio in the reactor; h2HC 0 Is a hydrogen-hydrocarbon ratio standard; hc_exp is the index of the hydrogen to hydrocarbon ratio factor term; cxMULT is a coefficient of coking rate of components with different carbon numbers, and the more the carbon number of the components is, the more easily the components are coked; [ CnHm ]]Is the mole fraction of the reactants.
S4: parameters in the catalytic reforming reaction model are calibrated.
The reforming reaction is a strong endothermic process, and a heating furnace is used to heat the stream to the temperature required for the reaction, one heating furnace being placed before each reactor. The calculation of the heating furnace takes into account the thermal efficiency, and the calculated fuel gas consumption is made to coincide with the actual one by correcting the relevant parameters.
The reactor is simulated by adopting an adiabatic plug flow reactor, and is solved by adopting a spline interpolation method, so that the size and the number of the division intervals can influence the solving efficiency of the reactor and the accuracy of a calculation result. All reactions occur simultaneously in the reactor, and after the dynamic parameters are calibrated, the model can accurately calculate the product composition, reaction temperature drop, pressure drop and catalyst coking amount. Further calculation can obtain WAIT, WABT, LHSV, WHSV parameters of reforming reaction.
The related calculation in the reaction module comprises parallel reaction distribution ratio calculation, pressure drop calculation, isomer distribution calculation and gasoline octane number calculation.
(1) Parallel reaction partition ratio calculation: the hydrogenolysis reaction, the naphthene dealkylation reaction, the hydrocracking reaction and the arene dealkylation reaction all have parallel reactions. The same group of parallel reactions are based on the same kinetic parameters, but the reactions are not carried out to the same extent, the generated C1, C2, C3 and C4 have a certain proportion, and the distribution ratio of each parallel reaction is determined by calibrating the corresponding parameters through the content of C1, C2, C3 and C4 in the product, and the parameters and the kinetic parameters are calibrated simultaneously.
(2) Pressure drop calculation: including the pressure drop across the reactor and the pressure drop across the reaction system.
The reactor pressure drop is calculated by the Ergun equation, which is suitable for calculating the pressure drop of a tubular reactor or conduit with a packed bed. The Ergun equation is as follows:
wherein U is apparent flow rate; epsilon is the bed void fraction; μ is the fluid viscosity; d (D) P Is the diameter of the catalyst particles; phi S Is the spherical factor of the catalyst particles; ρ is the fluid density.
The pressure drop of the reaction system refers to the pressure drop of the materials passing through a certain section of the process, such as the pressure drop generated by the materials passing through a heating furnace, a reactor and pipelines thereof, the pressure drop generated by the materials passing through a heat exchanger, a product separation tank and pipelines thereof, and the pressure drop generated by the materials passing through a compressor, a mixer and pipelines thereof. Since the model does not define the structural dimensions of the various devices and lines, the calculation of the system pressure drop reduces to a correlation with fluid flow and physical properties, introducing a pressure drop factor for parameter calibration. The system pressure drop correlation is as follows:
ΔP＝MOLF*MASF*MOLV*DPF
wherein MOLF is the molar flow of fluid; MASF is mass flow; MOLV is the molar volume; DPF is a pressure drop factor.
The parameters of the pressure drop calculation are calibrated under each working condition.
(3) Isomer distribution calculation: includes P 4 、P 5 And calculating isomers.
In the reforming reaction, the carbon four and carbon five alkanes are mainly products of hydrogenolysis reaction and hydrocracking reaction, normal structure and isomerism are not distinguished in the reaction expression, and the composition of isomerides is required to be analyzed in actual production.Thus, P produced by the reaction 4 ，P 5 Conversion to iP respectively 4 、nP 4 And iP 5 、nP 5 And (3) calibrating related parameters according to actual product analysis by establishing a correlation formula between the reaction temperature and the reaction temperature to obtain the proportion of each component.
Wherein, ISO_PERC is the proportion of isomers; T_AVG is the average temperature of the reactor; A. and B is a parameter, and calibration is carried out according to actual data.
(4) Gasoline octane number calculation: including RON and MON of reformate, and based on measurements of actual products, the relevant parameters are calibrated so that the octane number calculations of the model are consistent with the actual.
The model includes 301 reactions, 50 of which are reversible reactions, and the kinetic parameters that need to be corrected include pre-finger factors, activation energy, and equilibrium constants, 652 in total, which can be very difficult if all parameters are calibrated simultaneously. Because the same type of reaction has similar reaction characteristics, components with the same carbon number have similar reaction characteristics, and therefore, the pre-finger factors and the activation energy are treated to a certain degree.
(1) The adjustment of the pre-finger factor is performed by two types of parameters:
k 0 ＝k type ×k Ci ×k base
k base is a pre-finger factor reference value for each reaction, given at the time of establishing a reaction equation; k (k) type The reaction type is used as a reference adjustment parameter, the reaction type is further divided into single-branched paraffin isomerization, multi-branched paraffin isomerization, cyclization, ring expansion, dehydrogenation, hydrogenolysis, naphthene dealkylation, hydrocracking, arene dealkylation, polymerization, alkane coking, naphthene coking and arene coking, and 13 adjustment parameters are correspondingly set. k (k) Ci Is based on the carbon number of the reactant, and based on the previous 10 reaction types, the reactant under each reaction type has the inverse of the same carbon numberThe coking reaction is classified into one type, and is provided with 1 adjusting parameter, and coking reaction is provided with only one parameter, so that 62 parameters are provided in total.
By the method, the adjustment parameters of the pre-finger factors are simplified to 75, all the parameters do not need to be calibrated during parameter calibration, parameters with obvious influence on the reaction can be selected to be adjusted according to experience and actual conditions, and for example, 28 parameters are selected to be adjusted in the embodiment.
(2) The adjustment of the activation energy is based on the reaction type, which specifies the same activation energy, which is then reduced to 13 adjustment parameters. In general, the activation energy is not adjusted, and the activation energy is updated when the catalyst performance is greatly different.
(3) The equilibrium constant is not adjusted under the general condition, and the adjustment is only performed when the reaction result is greatly different from the actual reaction result and is greatly affected by the reaction equilibrium. The embodiment is directed to P 5 Equilibrium constant coefficient K of cyclization reaction par The adjustment is made.
In summary, after certain assumption and classification processing, 652 parameters are required to be calibrated and simplified into tens of parameters, so that the solving difficulty of the model is greatly reduced and the calculation speed is improved on the premise of not affecting the accuracy of the model. The kinetic parameters are updated according to the deactivation of the reforming reaction catalyst, generally for 3-6 months.
The activities calculated for the reforming reaction rate include global activity, individual reaction type activities, and catalyst activity.
Global active ACT global All reactions and reactor temperature drops are affected and calibrated simultaneously with the kinetic parameters.
ACT of each reaction type reac Means that a different activity is set according to different reaction types, and more activity is provided for coking reaction (COKEACT sys 、COKEACT rxi 、COKEACT reac ) Each activity only affects the corresponding type of reaction, the coking reaction related activity is calibrated under each working condition, and other reaction activities are not regulated under the general condition.
The catalyst activity includes catalyst preparationActive ACT cat ACT with acid site activity acid ACT with metal site activity metal . The overall activity of the catalyst integrates various factors affecting the activity of the catalyst, such as sulfur nitrogen poisoning, catalyst sintering, heavy metal pollution, mechanical damage, and the like. The activity of the acid site and the metal site affects the reaction occurring at the site, and is related to the coking content on the catalyst, and the correlation formula is as follows:
ACT site ＝A+B 1 ×COC+B 2 ×COC 2 +B 3 ×COC 3 +B 4 ×COC 4
in ACT site Represents an acidic site or a metallographic site activity; COC represents the coking rate on the catalyst; A. b (B) 1 、B 2 、B 3 、B 4 Is constant.
Catalyst activity is related to the amount of coking, and calibration is performed under each operating condition.
Through implementation of the steps, establishment of a catalytic reforming reaction model and calibration of parameters such as dynamics are completed, so that the model accords with the actual working condition of the production device. Simulation results of the reforming reaction net product and recycle hydrogen were compared with actual analysis data, as shown in table 3.
TABLE 3 comparison of the calculated results of the reforming reaction model with the actual values
| Composition of the composition | Simulation value, wt% | Actual value, wt% | Relative error, percent |
| H 2 | 3.8345 | 3.843 | -0.2207％ |
| P 1 | 0.4946 | 0.5 | -1.0840％ |
| P 2 | 0.9490 | 0.95 | -0.1087％ |
| P 3 | 1.4002 | 1.4 | 0.0164％ |
| iP 4 | 1.0684 | 1.066 | 0.2223％ |
| nP 4 | 0.7914 | 0.792 | -0.0780％ |
| iP 5 | 1.0934 | 1.101 | -0.6928％ |
| nP 5 | 0.5134 | 0.517 | -0.6928％ |
| C6 alkane | 9.9251 | 9.946 | -0.2060％ |
| C7 alkanes | 4.6915 | 4.696 | -0.0848％ |
| C8 alkanes | 0.9563 | 0.956 | 0.0322％ |
| C9 alkane | 0.1230 | 0.121 | 1.6603％ |
| C10+ alkanes | 0.0247 | 0.0237 | 4.2105％ |
| A 6 | 7.0505 | 7.007 | 0.6212％ |
| A 7 | 17.7629 | 17.75 | 0.0727％ |
| EB | 3.9180 | 3.918 | 0.0040％ |
| OX | 5.9110 | 5.911 | 0.0040％ |
| MX | 9.5472 | 9.547 | 0.0040％ |
| PX | 3.3498 | 3.350 | 0.0040％ |
| A 9 | 17.8348 | 17.84 | -0.0291％ |
| A 10+ | 7.4780 | 7.49 | -0.1599％ |
| 5N 5 | 0.4006 | 0.41 | -2.2971％ |
| 5N 6 | 0.5092 | 0.52 | -2.0690％ |
| 5N 7 | 0.0971 | 0.093 | 4.4104％ |
| 5N 8 | 0.1073 | 0.105 | 2.1600％ |
| Total amount of aromatic hydrocarbon | 72.8279 | 72.81 | 0.0246％ |
| Total of C5+ | 91.4619 | 91.44 | 0.0240％ |
| Purity of recycle hydrogen | 0.9052 | 0.9 | 0.5812％ |
As can be seen from the table, the simulation results of the main products such as aromatic hydrocarbon are basically consistent with the actual analysis values, and only C10+ alkane and naphthene have a certain error because of the small content. The model accuracy is sufficient to meet the modeling requirements of the reforming reaction. The model can be subsequently connected with the model of the re-contact and fractionation part to form a full-flow model of the continuous reforming device, and the full-flow model is deployed to an online optimization system to implement online real-time optimization.
Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (7)
1. A method of modeling a catalytic reforming reaction, comprising:
dividing the reaction mass into 58 lumped components based on lumped theory;
combining the division of the lumped components to establish a catalytic reforming reaction network;
according to the catalytic reforming reaction network, a catalytic reforming reaction model is established;
calibrating parameters in the catalytic reforming reaction model;
the establishing the catalytic reforming reaction model comprises the following steps:
material balance model of the reactor:
energy balance model of the reactor:
wherein u is the reactant flow linear velocity; z is the axial distance of the reactor; c A To the concentration of component A, RATE i The reaction rate of the ith reaction; x is X A,i Is the stoichiometric coefficient of component a in the ith reaction; ρ is the material density; c (C) P Is specific heat capacity; t is the reaction temperature; ΔH i Is the reaction heat of the ith reaction;
the 58 lumped components include:
alkane: 27, from C1 to C14, C12, C13, C14 do not distinguish normal and isomerism, C6, C7, C8 alkanes are divided into normal, mono-branched and multi-branched isomerism, C4, C5, C9, C10, C11 are divided into normal and isomerism;
cycloalkane: 16, from C5 to C14, C5 is only five-membered cycloalkane, C6 to C11 are divided into five-membered cycloalkane and six-membered cycloalkane, and C12, C13 and C14 are only expressed by cycloalkanes;
aromatic hydrocarbons: 13, from C6 to C14, C8 aromatics are further divided into ethylbenzene, ortho-xylene, meta-xylene and para-xylene;
and (3) coke: coKE, which means the COKE produced by the coking reaction, adheres to the catalyst;
hydrogen gas: h 2 ；
The establishing the catalytic reforming reaction model comprises the following steps:
for all reactions except coking reactions, a reaction rate equation was established:
wherein Rate is the reaction Rate; ACT (active transport protocol) global Is a global active factor; ACT (active transport protocol) cat Is the integral active factor of the catalyst; ACT (active transport protocol) site An active factor that is an acidic or metallic site; ACT (active transport protocol) reac Is a reaction type active factor; epsilon is the void ratio of the reactor bed; ρ P Is the catalyst particle density; p is the reaction pressure; p (P) 0 Is the reference pressure; p_exp is the index of the pressure factor phase; [ A ]]、[B]、[C]、[D]Is the partial pressure of the components; a. b, c and d are reaction metering coefficients; the fact is the pressure index of the driving force item; k (K) f Is a positive reaction rate constant; k (K) eq Is a balance constant;
for coking reactions, a reaction rate equation is established:
wherein CnHm is a component capable of coking reaction, including alkaneFive membered cycloalkanes and arenes; COKEACT sys Is an active factor of a reaction system; COKEACT rxi Is a reactor active factor; COKEACT reac The reaction type is active factors of coking reaction type, and the reaction type comprises alkane coking, naphthene coking and aromatic hydrocarbon coking; h2HC is the hydrogen-hydrocarbon ratio in the reactor; h2HC 0 Is a hydrogen-hydrocarbon ratio standard; hc_exp is the index of the hydrogen to hydrocarbon ratio factor term; cxMULT is a coefficient of coking rate of components with different carbon numbers, and the more the carbon number of the components is, the more easily the components are coked; [ CnHm ]]Is the mole fraction of the reactants.
2. The modeling method of catalytic reforming reaction according to claim 1, wherein the catalytic reforming reaction network comprises 301 kinetic reactions including 9 isomerization reactions, 26 cyclization reactions, 6 ring expansion reactions, 9 dehydrogenation reactions, 59 hydrogenolysis reactions, 35 naphthene dealkylation reactions, 79 hydrocracking reactions, 36 aromatics dealkylation reactions, 6 polymerization reactions, and 36 coking reactions.
3. The method of modeling a catalytic reforming reaction of claim 1, wherein calibrating parameters in the catalytic reforming reaction model comprises:
calibrating the factor before finger:
k 0 ＝k type ×k Ci ×k base ；
k base a pre-finger factor reference value for each reaction; k (k) type Is an adjustment parameter based on the reaction type; k (k) Ci The method is characterized in that the method takes the carbon atom number of a reactant as a reference adjustment parameter, the reactions of the reactant with the same carbon atom number under each reaction type are classified, 1 adjustment parameter is set, and only one adjustment parameter is set for coking reaction;
based on the reaction type, the same reaction type specifies the same activation energy for calibration of the activation energy.
4. The method of modeling a catalytic reforming reaction of claim 1, wherein calibrating parameters in the catalytic reforming reaction model comprises:
global activity in the reforming reaction, each reaction type activity, and catalyst activity were calibrated.
5. The method of modeling a catalytic reforming reaction of claim 1, wherein calibrating parameters in the catalytic reforming reaction model comprises:
the partition ratio of each parallel reaction was calibrated.
6. The method of modeling a catalytic reforming reaction of claim 1, wherein calibrating parameters in the catalytic reforming reaction model comprises:
the reactor pressure drop was calculated by the Ergun equation:
wherein U is apparent flow rate; epsilon is the bed void fraction; μ is the fluid viscosity; d (D) P Is the diameter of the catalyst particles; phi S Is the spherical factor of the catalyst particles; ρ is the fluid density;
the calculation of the pressure drop of the system is simplified into the correlation between the fluid flow and physical properties, the pressure drop factor is introduced for parameter calibration, and the correlation of the pressure drop of the system is as follows:
ΔP＝MOLF*MASF*MOLV*DPF
wherein MOLF is the molar flow of fluid; MASF is mass flow; MOLV is the molar volume; DPF is a pressure drop factor.
7. The method of modeling a catalytic reforming reaction of claim 1, wherein calibrating parameters in the catalytic reforming reaction model comprises:
by establishing a correlation with the reaction temperature, according to the actual product analysis, and calibrating related parameters, the proportion of each component is obtained:
wherein, ISO_PERC is the proportion of isomers; T_AVG is the average temperature of the reactor; A. and B is a parameter, and calibration is carried out according to actual data.
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