CN113053463B - Dynamic model modeling method for arene oxidation reaction and application of dynamic model - Google Patents
Dynamic model modeling method for arene oxidation reaction and application of dynamic model Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 230000000977 initiatory effect Effects 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000013461 design Methods 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000002474 experimental method Methods 0.000 claims description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011206 ternary composite Substances 0.000 claims description 4
- 238000009533 lab test Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000005457 optimization Methods 0.000 abstract description 5
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 98
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 90
- 230000003647 oxidation Effects 0.000 description 29
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000000376 reactant Substances 0.000 description 8
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 7
- -1 m-TALD Chemical compound 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 150000003254 radicals Chemical group 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012821 model calculation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- BYJQAPYDPPKJGH-UHFFFAOYSA-N 3-(2-carboxyethyl)-1h-indole-2-carboxylic acid Chemical compound C1=CC=C2C(CCC(=O)O)=C(C(O)=O)NC2=C1 BYJQAPYDPPKJGH-UHFFFAOYSA-N 0.000 description 1
- UHDNUPHSDMOGCR-UHFFFAOYSA-N 3-Formylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=O)=C1 UHDNUPHSDMOGCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 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
- G16C10/00—Computational theoretical chemistry, i.e. ICT specially adapted for theoretical aspects of quantum chemistry, molecular mechanics, molecular dynamics or the like
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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
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- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention relates to a dynamic model modeling method of an aromatic oxidation reaction and application of a dynamic model, wherein the modeling method comprises the following steps: in the process of preparing IPA or PTA by adopting MX or PX, obtaining a chain initiation reaction rate constant k 1 fit through experimental fitting; substituting k 1 fit into the dynamics model as k 1, searching the minimum value of the function S by using a lsqnonlin function, and calculating model parameters alpha and beta; substituting the calculated model parameters alpha and beta and different catalyst concentrations under actual production conditions into the dynamics model, and calculating to obtain a chain initiation reaction rate constant k 1 cal in actual production. The kinetic model established by the invention can quantitatively describe the influence of catalyst concentration and proportion on the oxidation reaction process under the industrial temperature and solvent ratio, and guide the design of an industrial reactor, the optimization of production operation conditions and the optimization of a production process.
Description
Technical Field
The invention relates to a model modeling method and a corresponding model in a chemical production process, in particular to a dynamic model modeling method and a dynamic model of aromatic hydrocarbon oxidation reaction.
Background
Isophthalic acid (Iso-PHTHALIC ACID, hereinafter referred to as IPA) and terephthalic acid (p-PHTHALIC ACID, hereinafter referred to as PTA) are relatively fast developing raw materials for organic chemical intermediates. Terephthalic acid is mainly used as a monomer of a PET polyester raw material. Isophthalic acid is mainly used as a modifying monomer of PET resin to improve the processing and product properties of PET resin; the method is used for replacing phthalic anhydride to produce high-strength chemical corrosion resistant unsaturated resin; and the alkyd resin with high performance and high solid content is produced by replacing phthalic anhydride. IPA has been widely used abroad, and has a promising development prospect, and many large companies are preparing to expand the production capacity and newly build IPA devices. As the scale of the device is continuously increased, the cost thereof is continuously reduced, and the application field and market share are continuously increased. The IPA in China has a certain foundation, and is applied to the fields of bottle-grade polyester resin, polyester cationic dyeable fiber, unsaturated resin and alkyd resin high-grade paint at present, but the sources of the IPA are mainly solved by import. As many large companies abroad use advanced technology to expand the capacity and newly build IPA devices, the competitiveness of these devices will be a big problem. The reaction process is fully known, and the establishment of a kinetic model of the reaction process has extremely important significance for guiding the production of isophthalic acid and terephthalic acid, so that the competitiveness of enterprises can be improved.
In industrial production, PX/MX oxidation reactions follow a free radical chain oxidation mechanism, and there are many intermediates in the reactions, for example, p (m) -methylbenzaldehyde (hereinafter, p (m) -TA), p (m) -methylbenzoic acid (hereinafter, p (m) -TA), p (m) -carboxybenzaldehyde (hereinafter, 4 (3) -CBA), and the like. It is generally believed that the oxidation of two methyl groups of PX/MX to alcohols, aldehydes, acids in turn in an oxidation process is a sequential, irreversible process:
In the prior art, the PX/MX oxidation reaction still comprises 30 reaction steps, although the catalytic reaction mechanism in the PX/MX oxidation process has been simplified to some extent. In the PX/MX oxidation reaction system, only the concentrations of 5 main components (PX, p-TALD, p-TA, 4-CBA, PTA and MX, m-TALD, m-TA, 3-CBA and IPA) can be obtained by sampling and accurately analyzing by liquid chromatography. The concentration of free radicals is difficult to quantitatively detect due to the unstable free base generated during the reaction. Estimating 30 model parameters with 5 observation variables, the estimated parameters are unreliable due to the large arbitrary nature, which is known as over-fitting, and it is therefore necessary to further reduce the model parameters to avoid over-fitting. At present, a plurality of scholars establish a reaction dynamics model, the model can well reflect the change of the concentration of reactants along with time, and the influence of the reaction temperature on the reaction can be predicted. However, the influence of the catalyst concentration and the proportion on the reaction is very complex, so far, no proper model can reflect and predict the influence of the catalyst concentration and the proportion on the reaction, and the optimization of an industrial reactor, production operation conditions and a production process is limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a dynamic model modeling method and a dynamic model for aromatic hydrocarbon oxidation reaction, which can quantitatively describe the influence of catalyst concentration and proportion on the oxidation reaction process.
The technical scheme for achieving the aim of the invention is as follows: the modeling method of the dynamic model of the arene oxidation reaction comprises the following steps:
s1: in the process of preparing IPA or PTA by MX or PX, obtaining a chain initiation reaction rate constant k1 fit (a kinetic reaction rate constant without adding catalyst concentration) through experimental fitting;
s2: substituting k 1 fit into the following formula as k 1, and searching the minimum of function S using the lsqnonlin function, calculating model parameters alpha and beta,
When MX is used, the formula used is:
when PX is used, the formula used is:
Wherein [ Co ], [ Mn ] and [ Br ] are the relative concentrations of cobalt catalyst, manganese catalyst and bromine promoter in the catalyst respectively, and k 1 is the chain initiation reaction rate constant (min-1);
S3: substituting the calculated model parameters alpha and beta and the different [ Co ], [ Mn ] and [ Br ] concentrations under actual production conditions into the formula (1) or (2), and calculating to obtain a chain initiation reaction rate constant k 1 cal in actual production.
PX reacted 1.69 times faster than MX due to the difference in reactivity of alkyl groups on PX and MX. Therefore, when the PX oxidation chain initiation reaction rate constant model is fitted, only α and β need to be obtained from the MX oxidation system, and the calculated k 1 value of MX (k 1 cal) is multiplied by 1.69, so that the calculated k 1 value of the PX oxidation chain initiation reaction rate constant of PX oxidation under the same reaction condition and operation (k 1 cal) can be calculated, that is, when the reaction condition and operation are the same, k 1 cal =1.69×k 1 cal of MX is calculated.
The lsqnonlin function may be a lsqnonlin function conventional in the art, preferably a lsqnonlin function in MATLAB, of the formula:
Wherein k 1,i cal and k 1,i fit are the chain initiation reaction rate constants determined by the formula and experimental fit, respectively, m is the total number of experiments, and the ordinal number i is 1 to m.
Preferably, in S1, k 1 fit obtained by experimental fitting is k 1 obtained by calculation using the following formula:
when the aromatic hydrocarbon is MX, the formula adopted is as follows:
C＝(k2CMX+k3Cm-TALD+k4Cm-TA+k5C3-CBA) (15)
wherein [ O ] MX、[O]m-TALD、[O]m-TA、[O]3-CBA is a peroxy radical derived from MX, m-TALD, m-TA, 3-CBA, respectively, and i and j in C i-O4-j independently represent alkyl or acyl;
When the aromatic hydrocarbon is PX, MX, m-TALD (m-tolualdehyde), m-TA (m-toluic acid), 3-CBA (3-carboxybenzaldehyde) and IPA in the formulas (4) - (15) are respectively replaced by PX, p-TALD, p-TA, 4-CBA and PTA;
C independently represents the molar mass ratio concentration (mol/kg) of the corresponding components in the reaction system, for example, the concentration of the substance MX is C m-MX, the concentration of the m-TALD is C m-TALD, the concentration of the m-TA is C m-TA, the concentration of the 3-CBA is C 3-CBA, the concentration of IPA is C IPA, the concentration of PX is C PX, the concentration of the p-TALD is C p-TALD, the concentration of the p-TA is C p-TA, the concentration of the 4-CBA is C 4-CBA, and the concentration of the PTA is C PTA;
dC/dt represents the reaction rate [ mol/(min. Kg) ] of each step, k1 represents the chain initiation reaction rate constant (min -1),k2-5 represents the chain transfer reaction rate constant [ kg/(mol. Min) ], and k 6 represents the chain termination reaction rate constant [ kg 2/(mol2. Min) ].
Further, the reaction rate constant k 1-k6 is obtained by reducing the sum of squares of residuals by the following formula:
wherein m is the total number of experiments, ordinal numbers i=1 to m, the number of experiments, ordinal numbers j=1 to 5, the components MX, m-tadd, m-TA, 3-CBA and IPA, or the components PX, p-tadd, p-TA, 4-CBA and PTA, And/>Calculated and measured values for the j-th component concentration, respectively. In the calculation, the concentrations C of the respective components are substituted into/>, in the formula (16)And (3) obtaining the product.
Preferably, in preparing IPA or PTA, the solvent is a mixture of acetic acid and water, the catalyst is a Co-Mn-Br ternary composite catalyst, the oxidant is air, and MX (meta-xylene) or PX (para-xylene) and the oxidant undergo catalytic oxidation reaction under the catalytic action of the catalyst in the solvent as follows:
the mass ratio of cobalt catalyst to manganese catalyst in the catalyst is 1:2-2:1 (e.g., 1:2, 1:1, or 2:1), and/or the mass ratio of the sum of the mass of cobalt catalyst and manganese catalyst to bromine promoter is 1:2-3:1 (e.g., 1:2, 1:1.5, 1:1, 3:2, 2:1, or 3:1), and/or the mass ratio concentration of bromine promoter in the reaction system is 350-1800ppm (e.g., 350ppm, 400ppm, 600ppm, 700ppm, 800ppm, 1200ppm, 1400ppm, or 1800 ppm).
The concentration (ppm) and the proportion of the cobalt catalyst, the manganese catalyst and the bromine promoter can be 800/400/1200、1200/600/1800、400/800/1200、400/400/1200、800/400/400、350/700/700、700/350/700、350/350/1400.
Preferably, the concentration of water in the solvent is 1% -15% by mass, for example 1%, 2%, 5%, 8%, 10%, 12% or 15%.
Further, the concentration of water in the reaction system is 6% to 8% by mass, for example, 6%, 7% or 8%, preferably 8%.
Preferably, the mass ratio of MX or PX to the solvent is from 1:5 to 1:3, e.g. 1:5, 1:4 or 1:3.
Preferably, the reaction temperature at which IPA or PTA is prepared is 448.2-466.2K, such as 448.2K, 450.2K, 453.15K, 456.2K, 458.2K, 463.2K, 465K or 466.2K, preferably 453.15K (180 ℃) and the reaction pressure is 1.1-1.3MPa, such as 1.1MPa, 1.2MPa or 1.3MPa (the reaction pressure is sufficient to maintain a vapor pressure above this threshold, no effect is exerted on the oxidation reaction, and only below this threshold will an effect be exerted on the oxidation reaction).
Preferably, the flow rate of the oxidizing agent in the preparation of IPA or PTA is 10-12L/min, for example 10L/min, 11L/min or 12L/min, preferably 12L/min. The oxygen concentration in the reaction has a critical value, and when the oxygen concentration is higher than the critical value, the oxidation reaction is not affected, and only when the oxygen concentration is lower than the critical value, the oxidation reaction is affected. Therefore, the air flow rate ensures that the oxygen concentration is greater than the critical value, and the consumption of the reaction is satisfied, namely the influence of the oxygen concentration is eliminated.
Catalytic oxidation reactions for MX or PX can be carried out in a reaction vessel conventional in the art, such as a semi-continuous reaction vessel. The stirring speed of the reaction vessel during the reaction may be a speed conventional in the art, for example 800rpm.
Any dynamic model of the aromatic hydrocarbon oxidation reaction disclosed by the invention can be obtained by adopting any dynamic model modeling method of the aromatic hydrocarbon oxidation reaction disclosed by the invention.
An application of a dynamic model of aromatic hydrocarbon oxidation reaction,
When the aromatic hydrocarbon is MX, the model formula is as follows:
when the aromatic hydrocarbon is PX, the model formula is:
Wherein [ Co ], [ Mn ] and [ Br ] are the relative concentrations of cobalt catalyst, manganese catalyst and bromine promoter in the catalyst, k 1 is the chain initiation reaction rate constant (min -1), and alpha and beta are model parameters.
Preferably, the model parameters α and β are obtained by substituting the experimentally fitted chain-initiated reaction rate constant into the model formula as k 1 and searching for the minimum calculation of the function S using the lsqnonlin function, the lsqnonlin function being
Wherein k 1,i cal and k 1,i fit are the chain initiation reaction rate constants determined by the model formula and experimental fitting, respectively, m is the total number of experiments, and the ordinal number i is 1 to m.
The kinetic model may be applied by using procedures conventionally used in the art, for example, the kinetic model calculation is performed on the chain initiation reaction rate constant k1 cal obtained by the modeling method, specifically, the kinetic parameters are obtained through laboratory experiments, and industrial reactor designs (such as reactor structure parameters of 80 cubes, 100 cubes and the like) with different sizes can be performed through the obtained kinetic parameters, so as to give operating conditions (suitable temperature, catalyst concentration and the like) with different terephthalic acid or isophthalic acid yield conditions.
The beneficial effects of the invention are as follows: the kinetic model established by the invention can quantitatively describe the influence of catalyst concentration and proportion on the oxidation reaction process at industrial temperature and solvent ratio, guide the design of an industrial reactor, the optimization of production operation conditions and the optimization of production process, solve the problem that the free radical kinetic model in the prior art is difficult to describe the influence of catalyst factors on the oxidation reaction, improve the advancement of the oxidation reaction kinetic model in the prior art, and have great guiding significance on the industrial MX/PX liquid phase oxidation process. The modeling method is suitable for establishing different types of alkyl aromatic hydrocarbon liquid phase oxidation kinetic models, and has wide applicability.
Drawings
FIG. 1 is a graph of experimental versus calculated values for the concentration of MX oxidation reactants and products at a catalyst Co/Mn/Br (ppm) of 800/400/1200 in example 1 of the present invention;
FIG. 2 is a graph of experimental versus calculated values for PX oxidation reactant and product concentrations for catalyst Co/Mn/Br concentrations (ppm) of 350/700/700 in example 2 of the present invention;
FIG. 3 is a graph of experimental versus calculated values for PX oxidation reactant and product concentrations for catalyst Co/Mn/Br concentrations (ppm) of 700/350/700 in example 2 of the present invention;
FIG. 4 is a graph of experimental versus calculated values for PX oxidation reactant and product concentrations for catalyst Co/Mn/Br concentrations (ppm) of 350/350/1400 in example 2 of the present invention.
Detailed Description
Example 1:
(1) Acquisition of experimental data
The industrial meta-xylene (MX) high-temperature catalytic oxidation process is carried out in a semi-continuous stirring bubbling kettle by taking a Co-Mn-Br ternary composite system as a catalyst, taking acetic acid-water (a mixture of acetic acid and water) as a solvent and taking air as an oxidant under the conditions that the reaction temperature is 180 ℃ (453.15K) and the reaction pressure is 1.2 Mpa.
The catalyst ratio is shown in Table 1, the air flow rate is 12L/min, the material MX is solvent (acetic acid-water) =1:5 (mass ratio), and the stirring speed of the reaction kettle is 800rpm. The water mass percentage concentration is 8%, the MX mass percentage concentration is 1/6 x 100%, and the acetic acid mass percentage concentration is (1-8% -1/6 x 100%).
The experiment is a batch reaction process, and the reaction time is 20min. During the experiment, the concentrations of MX, m-TALD, m-TA, 3-CBA and IPA were obtained by sampling at different times (1 min, 3min, 5min, 7min, 12min, 15min and 20 min). For example, the experimental results under 453.15K, [ Co ]/[ Mn ]/[ Br ] =800/400/1200 ppm are shown in fig. 1. Wherein, the points represent concentration experimental values, the lines represent concentration fitting values, and other concentration data are similar.
TABLE 1 Table MX Experimental reaction conditions for the catalytic Oxidation procedure
| Batch of | Temperature (K) | Reactants | H 2 O concentration (mass%) | Co/Mn/Br concentration (ppm) |
| 1 | 453.15 | MX | 8 | 400/400/1200 |
| 2 | 453.15 | MX | 8 | 400/800/1200 |
| 3 | 453.15 | MX | 8 | 1200/600/1800 |
| 4 | 453.15 | MX | 8 | 500/250/750 |
| 5 | 453.15 | MX | 8 | 800/600/1200 |
| 6 | 453.15 | MX | 8 | 800/400/1200 |
(2) Kinetic model construction
The differential equation of the free radical concentration of each component and the corresponding component in the semi-continuous reaction experiment along with the reaction time is shown as formulas (4) - (13):
Wherein:
C＝(k2CMX+k3Cm-TALD+k4Cm-TA+k5C3-CBA) (15)
The concentration value of the imported materials of each component:
t＝0,CMX＝CO MX,Cm-TALD＝0,Cm-TA＝0,C3-CBA＝0,CIPA＝0,
In the above formula, C i represents the concentration (mol/kg) of the corresponding component, dC i/dt represents the reaction rate [ mol/(min. Kg) ] of the corresponding step, k 1 represents the chain initiation reaction rate constant (min -1),k2-5 represents the chain transfer reaction rate constant [ kg/(mol. Min) ], and k 6 represents the chain termination reaction rate constant [ kg 2/(mol2. Min) ].
(3) Determining kinetic parameters of each step of reaction, and selecting an objective function
The acquired experimental data are subjected to parameter fitting by a kinetic model based on a free radical chain reaction, and a reaction rate constant k 1-k6 is obtained by reducing the sum of squares of residual errors by the following formula:
Wherein, Respectively representing calculated values and experimental values of a certain component, wherein 1-5 respectively represent substances MX, m-TALD, m-TA, 3-CBA and IPA, and m represents total experiment times carried out.
From the obtained concentration data, k 1-k6 calculated by the above fitting is shown in table 2.
TABLE 2 MX Rate constant fitting values for catalytic Oxidation Process with corresponding confidence interval Table (confidence 95%)
Thus, the parameters that can be shared, namely, k 2 to k 6, are listed in table 2, and only k 1 is the only variable parameter. As can be seen from table 1, all confidence intervals are at least 1 order of magnitude smaller than the corresponding rate constant, indicating that the rate constant is deterministic and reliable. Moreover, the chain propagation step proceeds faster than the chain initiation and termination steps, which is characteristic of typical free radical chain reactions. In particular, the rate constant of the chain initiation step is on the order of 10 -5, which is more sensitive to temperature changes. Clearly there is very good agreement between experimental data and model calculations from reactants to intermediates to main products.
(4) Model and parameter calculation including catalyst influencing factors
The model formula is:
wherein [ Co ], [ Mn ] and [ Br ] respectively represent the relative concentration of each element in the Co-Mn-Br catalyst.
The sum of squares of the difference in the initiation rate constant k 1 between the calculated and experimental fit values is minimized using the least squares method. The functions employed are as follows:
Wherein k 1,i cal and k 1,i fit represent the chain initiation rate constants determined by the model formula and fitting experiment, respectively; m=8 (indicating the total number of experiments). And the minimum of function S is searched using lsqnonlin functions (equation (3)) in MATLAB.
The values of alpha and beta are calculated to be 0.0022 and 0.0003 respectively.
(5) Verification
Comparison of MX oxidized chain initiation rate constants between the calculation method (model formula) and fitting experiments is shown in table 3:
TABLE 3 comparison of MX oxidized chain initiation Rate constants obtained using different methods
Model parameters: α=0.0022, β=0.0003.
Temperature: 453.15K.
It can be obtained that the model formula and modeling method thereof predict the fitting value of the experiment k 1 of MX catalytic oxidation.
Example 2:
(1) Acquisition of experimental data
The industrial Paraxylene (PX) high-temperature catalytic oxidation process is carried out in a semi-continuous stirring bubbling kettle by taking a Co-Mn-Br ternary composite system as an oxidant, taking acetic acid-water (a mixture of acetic acid and water) as a solvent and taking air as an oxidant under the conditions that the reaction temperature is 180 ℃ (453.15K) and the reaction pressure is 1.1MPa-1.3 MPa.
The catalyst ratios are shown in Table 4, the air flow rate is 12L/min, the material PX is solvent (acetic acid-water) =1:5 (mass ratio), and the stirring speed of the reaction kettle is 800rpm. The mass percentage concentration of water is 8%, the mass percentage concentration of PX is 1/6 x 100%, and the mass percentage concentration of acetic acid is (1-8% -1/6 x 100%).
The experiment is a batch reaction process, and the reaction time is 20min. During the experiment, samples were taken at different times (1 min, 3min, 5min, 7min, 12min, 15min and 20 min) to obtain the concentrations of PX, p-TALD, p-TA, 4-CBA and PTA, respectively.
Table 4 table of experimental reaction conditions for PX catalytic oxidation process
| Batch of | Temperature (K) | Reactants | H 2 O concentration (mass%) | Co/Mn/Br concentration (ppm) |
| 1 | 453.15 | PX | 8 | 700/350/700 |
| 2 | 453.15 | PX | 8 | 350/700/700 |
| 3 | 453.15 | PX | 8 | 350/350/1400 |
(2) Dynamics model construction, determination of dynamics parameters of each step of reaction, and selection of objective function
In the experimental process of PX, each component MX, m-TALD, m-TA, 3-CBA and IPA in the formulas (4) - (15) and (17) in the example 1 is replaced by PX, p-TALD, p-TA, 4-CBA and PTA, and the reaction rate constant k 1-k6 is obtained by calculating in the formula (16).
From the obtained concentration data, k 1-k6 calculated by the above fitting is shown in table 5.
TABLE 5 PX Rate constant fitting values for catalytic Oxidation Process with corresponding confidence interval Table (confidence 95%)
(3) Model and parameter calculation including catalyst influencing factors
Wherein [ Co ], [ Mn ] and [ Br ] respectively represent the relative concentration of each element in the Co-Mn-Br catalyst.
The square sum of the differences of the initiation rate constant k 1 between the calculated value and the experimental fit value is minimized by the least squares method using equation (3) in example 1.
The values of alpha and beta are calculated to be 0.0022 and 0.0003 respectively.
(4) Verification
PX reacted 1.69 times faster than MX due to the difference in reactivity of alkyl groups on PX and MX. Therefore, when the PX oxidation chain initiation constant model is fitted, the chain initiation rate constant k 1 of PX oxidation can be estimated by multiplying the MX oxidation system by α and β, which are obtained from the MX oxidation system.
As shown in table 6, there is very good agreement between the model predictions and the experimental fits, and the alpha and beta values of MX oxidation process can be successfully applied to PX oxidation process. The accuracy and transferability of the kinetic model of the present invention was verified.
TABLE 6 comparison of chain initiation Rate constants for PX oxidation obtained using different methods
Model parameters: α=0.0022, β=0.0003.
Temperature: 453.15K.
Referring to fig. 2-4, the px liquid-phase oxidation process also has good fitting precision, further illustrates the adaptability of the constructed dynamic model, and the constructed dynamic model containing the catalyst concentration can well predict the influence of the catalyst concentration and the mixture ratio on the reaction, and can effectively guide and optimize the industrial production process.
Claims (9)
1. A dynamic model modeling method for arene oxidation reaction is characterized by comprising the following steps:
s1: in the process of preparing IPA or PTA by adopting MX or PX, obtaining a chain initiation reaction rate constant k 1 fit through experimental fitting;
s2: substituting k 1 fit into the following formula as k 1, and searching the minimum of function S using the lsqnonlin function, calculating model parameters alpha and beta,
When MX is used, the formula used is:
when PX is used, the formula used is:
Wherein [ Co ], [ Mn ] and [ Br ] are the relative concentrations of cobalt catalyst, manganese catalyst and bromine promoter in the catalyst respectively, and k 1 is the chain initiation reaction rate constant;
S3: substituting the calculated model parameters alpha and beta and the different concentrations of [ Co ], [ Mn ] and [ Br ] under actual production conditions into the formula, and calculating to obtain a chain initiation reaction rate constant k 1 cal in actual production.
2. The method for modeling a kinetic model of an aromatic oxidation reaction according to claim 1, wherein said lsqnonlin function isWhere k 1,i cal and k 1,i fit are the chain initiation reaction rate constants determined by the formula and experimental fit, respectively, and m is the total number of experiments.
3. The modeling method of a kinetic model of an aromatic oxidation reaction according to claim 1 or 2, wherein when preparing IPA or PTA, the solvent is a mixture of acetic acid and water, the catalyst is a Co-Mn-Br ternary composite catalyst, the oxidant is air, the mass ratio of cobalt catalyst to manganese catalyst in the catalyst is 1:2-2:1, and/or the mass ratio of the sum of the mass of cobalt catalyst and manganese catalyst to bromine promoter is 1:2-3:1, and/or the mass ratio concentration of bromine promoter in the reaction system is 350-1200ppm.
4. A method of modeling a kinetic model of an aromatic oxidation reaction according to claim 3, wherein the concentration of water in the solvent is 1% -15% by mass.
5. The modeling method for a kinetic model of an aromatic oxidation reaction according to claim 4, wherein the mass percentage concentration of water in the reaction system is 6% -8%.
6. A method of modeling a kinetic model of an aromatic oxidation reaction according to claim 3, wherein the mass ratio of MX or PX to the solvent is 1:5-1:3.
7. The method for modeling a kinetic model of an aromatic oxidation reaction according to claim 3, wherein the reaction temperature is 448.2-466.2K and the reaction pressure is 1.1-1.3MPa when IPA or PTA is prepared.
8. A method for modeling a kinetic model of an aromatic oxidation reaction according to claim 3, wherein the flow rate of the oxidizing agent in the preparation of IPA or PTA is 10 "12L/min.
9. Use of a method for modeling a kinetic model of an aromatic oxidation reaction according to any one of claims 1-8, characterized in that kinetic parameters are obtained by laboratory experiments, and industrial reactor design is performed by means of the obtained kinetic parameters, giving operating conditions of different terephthalic acid or isophthalic acid yield conditions.
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