CN101260037A - Modeling method for alkylarene liquid phase oxidation dynamics mechanism model - Google Patents

Abstract

The invention relates to a modeling method for a dynamic mechanism model of alkyl aromatics liquid-phase oxidation. The invention is based on a free radical chain type reaction mechanism, simplifies the reaction path of alkyl aromatics liquid-phase oxidation, builds the dynamic mechanism model of alkyl aromatics liquid-phase oxidation, utilizes an internal mapping Newton method and iterates the adoption of conjugate gradient method for pretreatment every time to estimate parameters with which the dynamic model is involved, so as to realize the correct fitting and prediction of the model for actual data. The modeling method simplifies a chemical reaction model of alkyl aromatics liquid-phase oxidation, decreases model parameters, reduces the difficulty of estimating parameters, and provides convenience for industrial application. Moreover, the model has higher precision of fitting and predicting experimental data, thereby having good practicality. In addition, the modeling method is applicable to build the dynamic models of alkyl aromatics liquid-phase oxidation in different species, which has extensive applicability.

Description

A kind of modeling method of alkylarene liquid phase oxidation dynamics mechanism model

Technical field

The present invention relates to a kind of modeling method of alkylarene liquid phase oxidation dynamics mechanism model.

Background technology

Dynamics research is the basis of carrying out technology and engineering development.By investigating the influence of conditions such as temperature, concentration of component, catalyzer to reacting in the reaction process, be familiar with its rule and mechanism, set up the kinetic model of reaction process, can be for operational condition optimization, production technique improve, the design of industrial reactor and amplification etc. provide scientific basis.So the kinetic model of setting up the accurate description reaction process is significant.

The alkylaromatic hydrocarbon liquid-phase oxidation process is occupied critical role on chemical industry.For example, main raw material as polyester industrial---pure terephthalic acid (PTA, Purified Terephthalic Acid), the core of its production technique is p-Xylol (PX, p-Xylene) liquid-phase oxidation generates terephthalic acid (TPA, Terephthalic Acid).Equally, m-xylene liquid-phase oxidation system m-phthalic acid, trimethylbenzene liquid-phase oxidation system benzene tricarboxylic acid, toluene liquid-phase oxidation system phenylformic acid, ethylbenzene liquid-phase oxidation etc. also have consequence on chemical industry, they all follow identical reaction mechanism---free chain reaction.To accurately describe this alkylaromatic hydrocarbon liquid-phase oxidation process, have the difficulty of following three aspects:

At first, even because under hot conditions, the restriction on kinetics and the thermodynamics has all stoped alkylaromatic hydrocarbon and oxygen molecule (O ₂) direct reaction [Blackburn.Catalysis of Organic Reactions[M] .New York:Marcel Dekker, 1990], so usually by at alkylaromatic hydrocarbon and O ₂System in add Co and solvent HAc, thereby form certain metal oxygen complex.But under the katalysis of having only Co, product yield is very low, thereby adds HBr again and Mn (II) can increase Br in above-mentioned reaction system ^-And the transfer transport between the Co (III), the content of reduction Co (III).This can reduce the decarboxylation effect that Co (III) causes effectively, and helps improving temperature of reaction.But Co (II), Mn (II) and Br ^-Between the obvious co that exists can't be described with concrete relationship.

Secondly, the n level kinetic model that is commonly used to describe chemical reaction process this and inapplicable.For n level kinetic model, no matter n＞0 or n＜0, speed of reaction is along with the carrying out of reaction all is monotone increasing or successively decreases.And in the free chain reaction of reality, the quantity of the free radical in the initial reaction stage reaction system is few, speed of reaction is also less, along with reaction is carried out number of free radical and is increased gradually, speed of reaction presents elder generation's increase and reduces again at last, so n order reaction kinetic model has inborn defective when the liquid-phase oxidation of simulation or prediction alkylaromatic hydrocarbon.Simultaneously, because n order reaction kinetics is empirical in itself, also the model parameter that obtains can't be extrapolated in experiment condition situation in addition.

At last, produce a large amount of free radical and molecular product in the alkylaromatic hydrocarbon liquid phase oxidation reaction process.All free radical intermediates that relate in can't the detection reaction process with present technique means; In addition, when simulation comprises the oxidation reactor behavior of chemical reaction and mass transport affects, too Fu Za kinetic model will make reactor model can not find the solution owing to there being stiff problem.

Therefore, up to the present can't set up the succinct alkylaromatic hydrocarbon liquid phase oxidation reaction kinetics mechanism model that is applicable to industrial application, realize the correct match and the prediction of data.

Summary of the invention

In order to solve in the alkylaromatic hydrocarbon liquid phase oxidation reaction, because catalyzer is to reacting the complicacy that influences and can't producing a large amount of free radical and molecular product in the detection reaction process, and can't set up the problem of the succinct alkylaromatic hydrocarbon liquid phase oxidation reaction kinetics mechanism model that is fit to industrial application, the invention provides a kind of modeling method of alkylarene liquid phase oxidation dynamics mechanism model, mechanism based on free chain reaction, set up alkylaromatic hydrocarbon liquid-phase oxidation kinetic model, simplified the response path of alkylaromatic hydrocarbon liquid-phase oxidation, utilize inner mapping Newton method, and each iteration adopts pretreated method of conjugate gradient, estimate the related parameter of kinetic model, thereby realized correct match and the prediction of model for real data.

A kind of modeling method of alkylarene liquid phase oxidation dynamics mechanism model is characterized in that, described modeling method may further comprise the steps:

A) extract the related basic chemical reaction composition of alkylaromatic hydrocarbon liquid-phase oxidation process: reactant S, intermediate product I, the hydroperoxide of the reactant that produces in the reaction [O] _SHydroperoxide [O] with intermediate product _I, final product P has the peroxy radical i-OO of alkyl or acyl group Or j-OO

B) based on mechanism---the free chain reaction of alkylaromatic hydrocarbon liquid-phase oxidation, carry out modeling, model comprises following process:

1. chain initiation part: reactant and intermediate product react the hydroperoxide of distinguishing formation reaction thing and intermediate product with oxygen, promptly

" initiation " is chain initiation in the formula (1), K ₁, K ₁' be respectively the chain initiation rate constant of reactant and intermediate product;

2. chain transmitting portions: the hydroperoxide of reactant and intermediate product further react with oxygen and reactant, promptly

K in the formula (2) ₂, K ₂' be respectively [O] _S[O] _IWith the reaction rate constant that reactant S further reacts, k in the formula (3) ₃, K ₃' be respectively [O] _S[O] _IReaction rate constant with the further reaction of intermediate product I;

3. chain-terminating moiety: when two peroxy radical combinations that have alkyl or acyl group, promptly

I, j represent alkyl or acyl group, k in the reaction terminating then, formula (4) _iBe different peroxy radical-OO Between reaction rate constant;

C) simplifying model:

1. the chain initiation rate constant of reactant and intermediate product is considered as approximately equal in the part of b step, i.e. k ₁=k ₁', (1) formula is reduced to:

2. the partial reaction thing of b step and the peroxy radical of intermediate product are pressed isoreactivity and are handled, and reaction rate constant is equal, i.e. k ₂=k ₂', k ₃=k ₃', (3), (4) formula are reduced to:

3. the partial reaction thing of b step and the rate constant of termination between the different sorts peroxy radical are considered as equating being k ₄, (4) formula is reduced to:

D) estimation kinetics mechanism model parameter: for containing the ordinary differential equation group of 3～6 parameters, data use optimization method to obtain above-mentioned kinetic parameter to the kinetics mechanism model by experiment after simplifying.

The number of above-mentioned intermediate product I determined by the liquid phase oxidation reaction of reactant S, and has the oxygen partial pressure threshold value, when oxygen partial pressure surpasses threshold value, and reaction pair O ₂Show as zero level.Under the condition of the model parameter of having determined to relate to chain initiation, chain transmission and chain termination, as the condition of testing changes, chain initiation rate constant is the model parameter that unique needs redefine: when only changing temperature, in 100 degree, obtain chain initiation rate constant as temperature gap by extrapolation; When changing catalyzer composition branch or concentration or aqueous solvent content, chain initiation rate constant is estimated to obtain by experimental data.

Used optimization method during the estimated driving force mathematic(al) parameter be to adopt inner mapping Newton method, and each iteration adopts pretreated method of conjugate gradient in the described step d).

By the present invention, a kind of modeling method of alkylarene liquid phase oxidation dynamics mechanism model, this modeling method has been simplified the Chemical Reaction Model of alkylaromatic hydrocarbon liquid phase oxidation reaction, reduced model parameter, reduced the parameter estirmation difficulty, made things convenient for industrial application, and model all has higher precision to the match of experimental data and prediction, good practicality is arranged.In addition, this modeling method is applicable to the foundation of different types of alkylaromatic hydrocarbon liquid-phase oxidation kinetic model, has extensive applicability.

Description of drawings

Fig. 1 is the reaction path diagram that the PX liquid-phase oxidation generates TPA.

Fig. 2 is the comparison of each liquid phase component experimental value of PX liquid-phase oxidation product and model predication value, longitudinal axis concentration is the substrate concentration of each oxidation products, unit is mole/kg, transverse axis time is the time, unit is minute, discrete point composition curve is an experimental value in the figure, and continuous curve is a model predication value.

The reference numeral explanation:

Among Fig. 1, Fig. 2, PX is p-Xylene, i.e. p-Xylol; TALD is Tolualdehyde, that is: p-tolyl aldehyde; P-TA is p-Toluic Acid, that is: p-methylbenzoic acid; 4-CBA is 4-Carboxaldehyde, that is: to carboxyl benzaldehyde; PTA is Purified Terephthalic Acid, that is: pure terephthalic acid.

Embodiment

The present invention is further described below in conjunction with drawings and Examples.

Following example is an example with the reaction process that the PX liquid-phase oxidation under CATALYST Co/Mn/Br catalysis generates TPA, the modeling method of explaination alkylaromatic hydrocarbon liquid-phase oxidation kinetic model.

1. analyze the PX liquid-phase oxidation process, extract related chemical reaction composition.

Please refer to Fig. 1, i.e. PX liquid-phase oxidation process path.At first, methyl on the phenyl ring of reactant dimethylbenzene generates aldehyde, aldehyde radical generates carboxylic acid subsequently, and the oxidation of second methyl just takes place after first methyl is oxidized to carboxyl, therefore the intermediate product that generates in the reaction process has p-tolyl aldehyde (TALD, Tolualdehyde), p-methylbenzoic acid (p-TA, p-Toluic Acid), to carboxyl benzaldehyde (4-CBA, 4-Carboxaldehyde).

2. based on mechanism---the free chain reaction of alkylaromatic hydrocarbon liquid-phase oxidation, carry out modeling, model comprises following reaction process:

A) chain initiation:

Bromine atoms at first is initiated by following manner:

Mn ^III+Br ^-→Mn ^II+Br ^· (1)，

Bromine atoms is in case produce, with the α-H on the abstraction reaction thing RH:

Here, RH represents hydro carbons or aldehydes molecule.This step reaction belongs to chain initiation step, and its speed is far below the chain transmission that takes place subsequently.

B) chain transmission:

A. the generation of aldehyde

R With O ₂Reaction generates peroxy radical,

R ^·+O ₂→ROO ^·(3)，

The speed of reaction in this step is very fast, can think what moment took place.Then, the methyl on peroxy radical oxidation PX or the p-TA phenyl ring generates hydroperoxide.

Except in reaction, bromide anion being oxidized to atom, the carrying out of initiation reaction, the another one vital role of transition metal is by reducing the decomposition that activation energy quickens hydroperoxide.At Co ²⁺/ Mn ²⁺Exist down, ROOH is decomposed into corresponding product apace.For example, if ROOH from PX or p-TA, its degradation production will be TALD or 4-CBA:

ROOH+M ²⁺→R′CHO+H ₂O+M ²⁺ (5)。

B. Suan generation

The autoxidation of aldehyde and hydro carbons similar.Except chain initiation (formula 2), free acyl radical can also form through the following steps:

Free acyl radical generates the acyl peroxy radical further,

R′CO ^·+O ₂→R′COOO ^· (7)，

The same with step (3), this step reaction also is instantaneous.The acyl peroxy radical is attacked the α-H on the aldehyde radical, generates peroxy acid,

Peroxy acid passes through Co ²⁺Resolve into carboxylic acid,

R′COOOH+2Co ²⁺+2H ⁺→R′COOH+2Co ³⁺+H ₂O (9)，

α-H that the acyl peroxy radical also can be attacked on the hydro carbons forms peroxy acid,

C) chain termination:

When oxygen partial pressure surpasses 100torr, chain termination will only take place according to following manner:

In the formula (11), i, j represent alkyl or acyl group, and t represents the number of chain termination reaction equation.

3. model is simplified.

Although described reaction mechanism has been done simplification to a certain extent, 30 primitive steps have still been comprised.But have only 5 component concentrations to be detected in the PX liquid phase oxidation reaction system, go to estimate that with 5 observable variables 30 model parameters will make the parameter that obtains have very big arbitrariness.Therefore must further reduce model parameter so that parameter is more reliable.

At first, the different sorts peroxy radical is pressed the isoreactivity processing in the chain transmittance process; Secondly, the chain initiation rate constant of reactant and all intermediate products is considered as approximately equal; At last, the rate constant of termination between the different sorts peroxy radical is considered as equating.

According to above-mentioned rough handling, model parameter is reduced to 6, i.e. 1 chain initiation rate constant, 4 chain transfer rate constants and 1 rate constant of termination.Here, owing to relate to 3 intermediate products in this reaction system, the parameter of all models has 6.If when not having intermediate product in certain reaction system, it is 3 that model parameter will have only: i.e. 1 chain initiation rate constant, 1 chain transfer rate constant and 1 rate constant of termination.It is as follows that model is specifically established step:

A) foundation of model equation

Because reactions steps 3,5,7 and 9 is instantaneous, the path of mechanism reaction can be expressed as:

Here, [0] _PX, [0] _TALD, [0] _P-TAAnd [0] _4-CBARepresent by PX TALD, the superoxide that p-TA and 4-CBA produce respectively.

In addition, precedingly address, work as O ₂Dividing potential drop when surpassing a threshold value, reaction pair oxygen is zeroth order reaction.So the kinetic equation of PX liquid-phase oxidation can be expressed as follows:

$\frac{{\mathrm{dC}}_{\mathrm{PX}}}{\mathrm{dt}}=-k_1{C}_{\mathrm{PX}}-k_2{C}_{\left[O\right]}{C}_{\mathrm{PX}}---\left(17\right),$

$\frac{{\mathrm{dC}}_{\mathrm{TALD}}}{\mathrm{dt}}{=\mathrm{CC}}_{{\left[O\right]}_{\mathrm{PX}}}-k_1{C}_{\mathrm{TALD}}-k_3{C}_{\left[O\right]}{C}_{\mathrm{TALD}}---\left(18\right),$

$\frac{{\mathrm{dC}}_{p-\mathrm{TA}}}{\mathrm{dt}}{=\mathrm{CC}}_{{\left[O\right]}_{\mathrm{TALD}}}-k_1{C}_{p-\mathrm{TA}}-k_4{C}_{\left[O\right]}{C}_{p-\mathrm{TA}}---\left(19\right),$

$\frac{{\mathrm{dC}}_{4-\mathrm{CBA}}}{\mathrm{dt}}={\mathrm{CC}}_{{\left[O\right]}_{p-\mathrm{TA}}}=k_1{C}_{4-\mathrm{CBA}}-k_5{C}_{\left[O\right]}{C}_{4-\mathrm{CBA}}---\left(20\right),$

$\frac{{\mathrm{dC}}_{\mathrm{TPA}}}{\mathrm{dt}}={\mathrm{CC}}_{{\left[O\right]}_{4-\mathrm{CBA}}}---\left(21\right),$

$\frac{{\mathrm{dC}}_{{\left[O\right]}_{\mathrm{PX}}}}{\mathrm{dt}}=k_1{C}_{\mathrm{PX}}+k_2{C}_{\left[O\right]}{C}_{\mathrm{PX}}-{\mathrm{CC}}_{{\left[O\right]}_{\mathrm{PX}}}-k_6{C}_{{\left[O\right]}_{\mathrm{PX}}}(C_{\left[O\right]}+C_{{\left[O\right]}_{\mathrm{PX}}})---\left(22\right),$

$\frac{{\mathrm{dC}}_{{\left[O\right]}_{\mathrm{TALD}}}}{\mathrm{dt}}=k_1{C}_{\mathrm{TALD}}+k_3{C}_{\left[O\right]}{C}_{\mathrm{TALD}}-{\mathrm{CC}}_{{\left[O\right]}_{\mathrm{TALD}}}-k_6{C}_{{\left[O\right]}_{\mathrm{TALD}}}(C_{\left[O\right]}+C_{{\left[O\right]}_{\mathrm{TALD}}})---\left(23\right),$

$\frac{{\mathrm{dC}}_{{\left[O\right]}_{p-\mathrm{TA}}}}{\mathrm{dt}}=k_1{C}_{p-\mathrm{TA}}+k_4{C}_{\left[O\right]}{C}_{p-\mathrm{TA}}-{\mathrm{CC}}_{{\left[O\right]}_{p-\mathrm{TA}}}-k_6{C}_{{\left[O\right]}_{p-\mathrm{TA}}}(C_{\left[O\right]}+C_{{\left[O\right]}_{p-\mathrm{TA}}})---\left(24\right),$

$\frac{{\mathrm{dC}}_{{\left[O\right]}_{4-\mathrm{CBA}}}}{\mathrm{dt}}=k_1{C}_{4-\mathrm{CBA}}+k_5{C}_{\left[O\right]}{C}_{4-\mathrm{CBA}}-{\mathrm{CC}}_{{\left[O\right]}_{4-\mathrm{CBA}}}-k_6{C}_{{\left[O\right]}_{4-\mathrm{CBA}}}(C_{\left[O\right]}+C_{{\left[O\right]}_{4-\mathrm{CBA}}})---\left(25\right),$

$\frac{{\mathrm{dC}}_{i-O_4-j}}{\mathrm{dt}}=k_6({C_{\left[O\right]}}^2-C_{{\left[O\right]}_{\mathrm{PX}}}{C}_{{\left[O\right]}_{\mathrm{TALD}}}-C_{{\left[O\right]}_{\mathrm{PX}}}{C}_{{\left[O\right]}_{p-\mathrm{TA}}}-C_{{\left[O\right]}_{\mathrm{PX}}}{C}_{{\left[O\right]}_{4-\mathrm{CBA}}}-C_{{\left[O\right]}_{\mathrm{TALD}}}{C}_{{\left[O\right]}_{p-\mathrm{TA}}}$

$-C_{{\left[O\right]}_{\mathrm{TALD}}}{C}_{{\left[O\right]}_{4-\mathrm{CBA}}}-C_{{\left[O\right]}_{p-\mathrm{TA}}}{C}_{{\left[O\right]}_{4-\mathrm{CBA}}})---\left(26\right).$

In above-mentioned kinetic model equation (17)～(26), C represents reactant and all concentration of intermediate products sums;

C _[0]Represent all peroxy radical concentration sums.

Starting condition is: t=0,

C _PX＝C ⁰ _PX；C _TALD＝0；C _p-TA＝0；C _4-CBA＝0；C _TPA＝0；C _[0]PX＝0；C _[0]TALD＝0；C _[0]p-TA＝0；C _[0]4-CBA＝0；C _i-04-j＝0

(27)。

4. estimate the kinetics mechanism model parameter.

At first construct the objective function of estimation model parameter, adopt the mode of calculated value and observed value sum of squares of residues minimum here, be shown below:

$s=\underset{i=1}{\overset{m}{\mathrm{\Σ}}}\underset{j=1}{\overset{5}{\mathrm{\Σ}}}{(y_{\mathrm{ij}}^{\mathrm{cal}}-y_{\mathrm{ij}}^{\exp })}^2---\left(28\right),$

Wherein, y _{I, j} ^ExpAnd y _Ij ^CalObserved value and the calculated value of representing j liquid phase component concentration in i the experimental point respectively.

Learning mechanism model parameter k by the optimization technique estimated driving force ₁～k ₆The time, adopt inner mapping Newton method, and each iteration adopts pretreated method of conjugate gradient.All will find the solution when iteration each time once with the ordinary differential equation group of initial value problem, promptly formula (17)～(26) adopt four-five rank runge kutta methods to the equation group inte gration here.

At the PX liquid-phase oxidation, carry out following dynamic experiment: the 550mL that at first packs in volume is the batch reactor of 1L comprises the liquid phase miscellany of reaction solvent HAc, reactant PX, CATALYST Co/Mn/Br; Closed reactor then, (temperature to 150～250 ℃, pressure to 1.0～2.0MPa) the back bubbling air carries out oxidizing reaction, (0.5～5 minute) sampling every at set intervals to wait to heat up, be pressurized to certain condition; At last, the pending laggard chromatogram of sample is analyzed, and obtains the time dependent experimental data of each concentration of component of liquid product.Utilize formula (28), can estimate the numerical value of kinetic parameter in conjunction with experimental data and kinetic model.Following table has been listed one group of kinetic parameter estimated value of PX liquid-phase oxidation under certain reaction conditions, is 95% by the confidence level of estimated parameter.

The parameter of utilizing estimation to obtain has been predicted certain catalyst concn, 200 ℃ of curves that descend each liquid phase component concentration changes with time, and contrasts with experimental value, and concrete curve ratio sees also Fig. 2, as seen has degree of precision.

Above-mentioned modeling method not only is applicable to sets up the dynamic (dynamical) mechanism model of PX liquid phase oxidation reaction, is suitable for too for other alkylaromatic hydrocarbon liquid-phase oxidation kinetic models.

Only for the preferred embodiment of invention, be not to be used for limiting practical range of the present invention in sum.Be that all equivalences of doing according to the content of the present patent application claim change and modification, all should be technology category of the present invention.

Claims (7)

1. the modeling method of an alkylarene liquid phase oxidation dynamics mechanism model is characterized in that, described modeling method may further comprise the steps:

A) extract the related basic chemical reaction composition of alkylaromatic hydrocarbon liquid-phase oxidation process: reactant S, intermediate product I, the hydroperoxide of the reactant that produces in the reaction [O] _sHydroperoxide [O] with intermediate product _I, final product P has the peroxy radical i-OO of alkyl or acyl group Or j-OO

B) based on mechanism---the free chain reaction of alkylaromatic hydrocarbon liquid-phase oxidation, carry out modeling, model comprises following process:

1. chain initiation part: reactant and intermediate product react the hydroperoxide of distinguishing formation reaction thing and intermediate product with oxygen, promptly

" initiation " is chain initiation in the formula (1), k ₁, k ₁' be respectively the chain initiation rate constant of reactant and intermediate product;

2. chain transmitting portions: the hydroperoxide of reactant and intermediate product further react with oxygen and reactant, promptly

K in the formula (2) ₂, k ₂' be respectively [O] _s[O] _IWith the reaction rate constant that reactant S further reacts, k in the formula (3) ₃, k ₃' be respectively [O] _s[O] _IReaction rate constant with the further reaction of intermediate product I;

3. chain-terminating moiety: when two peroxy radical combinations that have alkyl or acyl group, promptly

I, j represent alkyl or acyl group, k in the reaction terminating then, formula (4) _iBe different peroxy radical-OO Between reaction rate constant;

C) simplifying model:

1. the chain initiation rate constant of reactant and intermediate product is considered as approximately equal in the part of b step, i.e. k ₁=k ₁', (1) formula is reduced to:

2. the part of b step, the peroxy radical of reactant and intermediate product is pressed isoreactivity and is handled, and reaction rate constant is equal, i.e. k ₂=k ₂', k ₃=k ₃', (3), (4) formula are reduced to:

3. the part of b step, the rate constant of termination between reactant and the different sorts peroxy radical are considered as equating being k ₄, formula (4) is reduced to:

D) estimation kinetics mechanism model parameter: for containing the ordinary differential equation group of 3～6 parameters, data use optimization method to obtain above-mentioned kinetic parameter to the kinetics mechanism model by experiment after simplifying.

2. by the modeling method of the described a kind of alkylarene liquid phase oxidation dynamics mechanism model of claim 1, it is characterized in that: the number of intermediate product I is determined by the liquid phase oxidation reaction of reactant S.

3. by the modeling method of the described a kind of alkylarene liquid phase oxidation dynamics mechanism model of claim 1, it is characterized in that: there is the oxygen partial pressure threshold value, when oxygen partial pressure surpasses threshold value, reaction pair O ₂Show as zero level.

4. by the modeling method of the described a kind of alkylarene liquid phase oxidation dynamics mechanism model of claim 1, it is characterized in that: under the condition of the model parameter of having determined to relate to chain initiation, chain transmission and chain termination, as the condition of testing changes, and chain initiation rate constant is the model parameter that unique needs redefine.

5. by the modeling method of the described a kind of alkylarene liquid phase oxidation dynamics mechanism model of claim 4, it is characterized in that: when only changing temperature, in 100 degree, obtain chain initiation rate constant by extrapolation as temperature gap.

6. by the modeling method of the described a kind of alkylarene liquid phase oxidation dynamics mechanism model of claim 4, it is characterized in that: when changing catalyzer composition branch or concentration or aqueous solvent content, chain initiation rate constant is estimated to obtain by experimental data.

7. by the modeling method of the described a kind of alkylarene liquid phase oxidation dynamics mechanism model of claim 1, it is characterized in that: used optimization method during the estimated driving force mathematic(al) parameter in the described step d), be to adopt inner mapping Newton method, and each iteration adopt pretreated method of conjugate gradient.