CN108375905A - A kind of segmented charge ratio course control method for use based on activation energy analysis - Google Patents

A kind of segmented charge ratio course control method for use based on activation energy analysis Download PDF

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CN108375905A
CN108375905A CN201810195109.3A CN201810195109A CN108375905A CN 108375905 A CN108375905 A CN 108375905A CN 201810195109 A CN201810195109 A CN 201810195109A CN 108375905 A CN108375905 A CN 108375905A
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reaction
charge ratio
activation energy
control method
segmented
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袁建华
陈庆
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China Three Gorges University CTGU
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    • G05CONTROLLING; REGULATING
    • G05BCONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
    • G05B13/00Adaptive control systems, i.e. systems automatically adjusting themselves to have a performance which is optimum according to some preassigned criterion
    • G05B13/02Adaptive control systems, i.e. systems automatically adjusting themselves to have a performance which is optimum according to some preassigned criterion electric
    • G05B13/04Adaptive control systems, i.e. systems automatically adjusting themselves to have a performance which is optimum according to some preassigned criterion electric involving the use of models or simulators
    • G05B13/042Adaptive control systems, i.e. systems automatically adjusting themselves to have a performance which is optimum according to some preassigned criterion electric involving the use of models or simulators in which a parameter or coefficient is automatically adjusted to optimise the performance

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Abstract

The present invention relates to a kind of segmented charge ratio course control method for use based on activation energy analysis based on the analysis of composite chemical reaction activity in chemical process, to determine that main reaction is different from reaction occurrence degree of the side reaction under condition of different temperatures first;Then according to the technological process of production, Chemical Manufacture model and PCS7 automatic control systems based on SMPT 1000 are established, and emulation experiment is carried out to model;It is final to determine, the reactant of three different temperatures sections, the different feeds ratio of catalyst.Present invention determine that segmented charging ratio method compared with the fixed charging ratio method of tradition, can accelerating chemical production process reaction rate, improve product reaction conversion ratio.

Description

A kind of segmented charge ratio course control method for use based on activation energy analysis
Technical field
The present invention relates to continuous chemical process control fields, and in particular to a kind of segmented based on activation energy analysis Charge ratio course control method for use.
Background technology
In actual chemical process, there is higher requirement to reaction conversion ratio and reaction rate.It can use most The short time reaches the concentration of requirement and the production of held stationary, can not only improve product yield, save the production time, moreover it is possible to Effectively save production cost.The chemical reaction of production technology is all often recombination reaction, and there is major and minor two parallel competitions Reaction, side reaction generate substance be purpose product impurity, therefore reasonably control it is major and minor reaction a situation arises, for carrying High reaction conversion ratio is very effective with reaction rate.
Conventional method often fixed charge proportion, and in chemical process the differential responses stage parameter characteristic, it is right Reactant concentration ratio, catalyst amount have different requirements.Due to main reaction, the exothermic heat of reaction amount of side reaction, pre-exponential factor, The difference of the parameters such as activation energy, in the same warming-up section, the occurrence degree of main reaction and side reaction is also different.Actual production In the process, reaction-ure feeding than, influence of the catalyst amount to reaction process is coupling and interactional, considers reaction Process different phase and its response characteristic, and configure different chargings when corresponding catalyst amount, the control to reaction process System is advantageously.
Invention content
The purpose of the present invention is to provide a kind of segmented charge ratio course control method for use based on activation energy analysis, to change Into the shortcoming of conventional feeds method.
A kind of segmented charge ratio course control method for use based on activation energy analysis, includes the following steps:
1) index parameter reacted according to composite chemical in reactor, including main reaction heat release, main reaction pre-exponential factor, master Reaction activity, side reaction heat release, side reaction pre-exponential factor, side reaction activation energy, initial temperature, in conjunction with Arrhenius relationship FormulaAnalysis, when main reaction activation energy is less than side reaction activation energy, promotes temperature quickening reaction rate, The velocity coefficient of side reaction increases bigger, and side reaction is easier to occur, and wherein k is reaction rate, and R is molar gas constant, and T is Temperature, k0And EaIt is two empirical parameters, parameter and activation energy before respectively referring to;
Specifically, according to Arrhenius relational expression:
Wherein, k is reaction rate, and R is molar gas constant, and T is temperature, k0And EaIt is two empirical parameters, respectively refers to Preceding parameter and activation energy, generally by measuring, relevant parameter is as shown in table 1.
Formula (1) is taken into logarithm, is obtained:
Wherein, k (T1) and k (T2) it is in temperature T respectively1And T2Under reaction velocity coefficient.
Clearly for the different reaction of activation energy, warming-up section T2-T1In the case of identical, EaBigger, reaction rate is faster. Main reaction (reaction rate k1, activation energy Ea1) and side reaction (reaction rate k2, activation energy Ea2) it is two parallel competing Reaction is striven, can be obtained by formula (2):
Work as Ea2> Ea1(main reaction activation energy is less than side reaction activation energy), reaction temperature T2> T1, perseverance is on the right of formula (3) It is negative, thenI.e. main reaction rate is less than rate of side reactions.It is determined according to the difference of activation energy, main reaction Rate, rate of side reactions with temperature rise relationship.
2) with fixed charging ratio method emulation experiment temperature segmentation condition, division points;Warming-up section is reacted to divide.
Specifically, reactor Semi-physical model is a part for SMPT-1000 process control experiment platforms, can be completely real Chemical reaction process under existing different parameters.Experiment porch simulation reaction object is controlling centainly anti-under traditional control method After answering temperature and the fixed catalyst amount of input, controlled using single charge ratio to accelerate reaction process.Analysis conventional side Chemical reaction process reactor heating experimental data under case.In the case of obtaining different temperatures, main reaction, side reaction reaction rate It is different, determines the reaction warming-up section division points of Discrete control.
3) two section type charge ratio or three-stage is used to feed ratio method;
Specifically, the proposition of segmented course control method for use.
Traditional scheme is improved to adapt to the change charge ratio control of reaction temperature variation.It is proposed two kinds of improvement projects:
Scheme one, two section type charge ratio, temperature rise period charge ratio adapt to side reaction;Stage of reaction charge ratio adapts to master Reaction occurs.
Since in actual production process, material inlet valve to reactor needs to transmit by pipeline, so changing charge ratio simultaneously The problem of cannot influencing to react, lag in existence time rapidly.Therefore, it proposes that transition stage is added on the basis of scheme one Scheme two, three-stage charge ratio, temperature rise period charge ratio adapt to side reaction;The side reaction of transition stage charge ratio is to main reaction Transition;Stage of reaction charge ratio adapts to main reaction.
4) determine that adaptation is respectively configured in the Discrete control of catalyst amount, temperature rise period, the stage of reaction according to emulation experiment The catalyst amount of different phase;
Catalyst is at a temperature of differential responses to the influence of reaction difference, shadow of the different catalyst amounts to same reaction Sound is different.Requirement of the characteristic in differential responses stage to catalyst amount is also different.It is main during the chemical reaction Reaction is obviously different the dosage of catalyst with side reaction, and catalyst amount will be divided by emulation platform experimental data Duan Youhua.The catalyst amount for adapting to different phase is respectively configured in temperature rise period, the stage of reaction.
5) establish Chemical Manufacture model and automatic control system, establish Chemical Manufacture model based on SMPT-1000 and PCS7 automatic control systems carry out experimental verification.
Preferably, composite chemical reaction is that there are the parallel reactions of parallel competitive relation with side reaction for main reaction.
It is further preferred that the recombination reaction is more two kinds of reactants, a kind of reaction of catalyst proportion, main product is generated Object and by-product, wherein principal product are purpose product.
It is further preferred that the indicator reaction parameter of the step 1) main reaction and side reaction is measured by experiment.
It is further preferred that the step 2) specific method is:It is controlling certain reaction temperature and is putting into fixed urge After agent dosage, controlled using single charge ratio to accelerate reaction process, chemical reaction process reaction under analysis conventional scheme Device heat up experimental data, in the case of obtaining different temperatures, main reaction, side reaction reaction rate be it is different, determine segmentation The reaction warming-up section division points of control.
It is further preferred that the automatic control system that the method is established is programmed by PCS7 and is realized.
It is further preferred that the technological process of the compounded chemical reaction is modeled and is carried out in SMPT-1000 experiment porch Emulation experiment is verified.
Preferably, step 3) the two section type charge ratio is that temperature rise period charge ratio adapts to side reaction, the stage of reaction Charge ratio adapts to main reaction;Three-stage charge ratio is that temperature rise period charge ratio adapts to side reaction, transition stage charging Than side reaction to main reaction transition, stage of reaction charge ratio adapts to main reaction.
Advantageous effect of the present invention:
1, using the different feeds in adaptation differential responses stage than mode, reaction conversion ratio improves 2.485%, reaches and sets The time of constant temperature degree shortens 35s (i.e. reaction rate is accelerated), and the time for reaching requirement concentration value shortens 252s, increases production Object cumulant.
2, transition stage is added, eliminates and changes the problem of charge proportion influences to lag on the reaction time, further carry High reaction rate increases yield.
3, compared with traditional scheme (single charge ratio mode), reduce the invalid of raw material in the starting stage of Chemical Manufacture The waste used can be that the production process is cost-effective.
Description of the drawings
Fig. 1 chemical reaction technical process
Fig. 2 segmented control flow charts
Fig. 3 different schemes reaction temperatures TI1103 (i.e. reaction rate) curve graph
Fig. 4 different schemes production concentrations AI1101 (i.e. reaction conversion ratio) curve graph
Specific implementation mode
With reference to specific embodiment, further details of elaboration is made to the present invention, but embodiments of the present invention are not It is confined to the range of embodiment expression.These embodiments are merely to illustrate the present invention, range and is not intended to limit the present invention.This Outside, after reading present disclosure, those skilled in the art can various modifications may be made to invention, these equivalent variations are same Fall within the appended claims limited range of the present invention.
Embodiment 1
With reference to the flow for emulating practical chemical production technology, the segmented analyzed the present invention is based on activation energy is fed It is described in detail than course control method for use.
Such as Chemical Manufacture reaction process:For known exothermal reaction process under catalyst C effects, raw material A, B reactions generate master Product D (required product) and by-product E (impurity), major and minor reaction is strong exothermal reaction, and reaction equation is as follows:
Main reaction:
Side reaction:
Add in addition to control catalyst C dosages, control reactor characterisitic parameter (temperature, pressure etc.) in above-mentioned Chemical Manufacture Outside fast response rate, or even higher D products reaction conversion ratio can be also obtained using the excessive technique of raw material A and (refers to technique Match A:B:C is 9:3:1), therefore rationally adjusting raw material A, B ratios and catalyst C dosages are extremely important.Above-mentioned work production reaction Device mathematical model part index number parameter is as shown in table 1.
1 reactor index parameter of table
Analysis is found:There are problems that cut-throat competition in reaction process between main reaction and side reaction, it can be seen that main reaction Activation energy is less than side reaction activation energy (side reaction activation energy is 2.32 times of main reaction activation energy), and main reaction pre-exponential factor is more than Side reaction pre-exponential factor, main reaction heat release are more than side reaction heat release.
According to the above-mentioned Chemical Manufacture of activation energy correlation analysis, main reaction activation energy is less than side reaction activation energy, promotes temperature When accelerating reaction rate, the velocity coefficient of side reaction increases bigger.In reaction process, reaction temperature is promoted to main reaction rapidly Temperature condition, be conducive to improve reaction rate, increase product accumulation, improve yield.Initial temperature-rise period production concentration compared with Low, this stage, activation energy was analysis shows this stage side reaction is more sensitive to temperature mainly to be promoted based on reaction temperature.Initially Stage should reduce the extra raw material A for having neither part nor lot in reaction, and (20 DEG C) A of room temperature excessively can make heating rate slack-off, lead to main reaction It cannot occur rapidly.
It is controlled using single charge ratio to accelerate reaction process.In aforementioned chemical process, control charge ratio is A: B:C is equal to 9:3:1.Chemical reaction process reactor heating experimental data is as shown in table 2 under traditional scheme.Different temperatures situation Under, main reaction, side reaction reaction rate be different.
2 reactor of table heating data
Data in table 2 are analyzed, temperature of reactor heating from 20 DEG C to 40 DEG C is relatively slow (about 415s), from 40 DEG C to 60 DEG C of heatings are very fast (about 163s).When analysis can determine about 45 DEG C, the reaction rate of main reaction is obviously accelerated, and temperature is may be set to Spend segmentation condition.
It is tested on reactor Semi-physical model according to segmented feed process, only change catalyst C during this Dosage.The influence that experiment mainly reacts different phase by measuring different catalysts dosage, it is opposite to measure catalyst Optimal dosage, when will heat up the division points of stage and the stage of reaction to be set in temperature of reactor being 45 DEG C.Experimental data such as table 3 Shown, temperature of reactor TI1103 can characterize reaction rate, production concentration AI1101 can characterize reaction conversion ratio.
Experimental data under 3 different catalysts of table proportioning
Comprehensive comparative analysis can obtain temperature rise period relatively optimal A:B:C is 1:1:0.1667;The stage of reaction is relatively optimal A:B:C is 1:0.33:0.0526.Catalyst amount adapts to the Discrete control method of different phase reaction, can significantly improve Reaction rate and conversion ratio.
To sum up, three kinds of catalyst amounts and charge ratio control program, as shown in table 4.
4 catalyst amount of table and charge ratio control program
Scheme one is determined as 20-30 DEG C of temperature rise period, 30-100 DEG C of the stage of reaction;Scheme two is determined as temperature rise period 20- 30 DEG C, 30-45 DEG C of transition stage, 45-100 DEG C of the stage of reaction.
Chemical production technology model foundation based on SMPT-1000, raw material A are entered by feed pump mixed respectively with raw material B In-tank mixing is closed, valve FV1101 and valve FV1102 controls the flow of A, B charging respectively.Mixture enters reactor and is put Thermal response, catalyst C are added from reactor head, and FV1104 adjusts the flow of C.Technical process is as shown in Figure 1.Reaction rate, Conversion ratio and reaction temperature, pressure, material and catalyst mixing match etc. are related.Measurement of concetration is installed after outlet valve FV1106 Device measures the reaction conversion ratio AI1101 of technical process.Major and minor reaction is exothermic reaction, and reaction rate speed can be by anti- Device temperature TI1103 is answered to rise speed to weigh.
When studying charge ratio control method, the aperture for only changing valve FV1101, FV1102 controls A, B feed rate (quality=flow * times);Change the flow of FV104 apertures control catalyst C.Process parameters parameter:Blending tank liquid level 30%; 100 DEG C of temperature of reactor, liquid level 50%;Flash tank pressure 40KPa, liquid level 10%;Rate of discharge 9.5kg/s;Outlets products are dense Degree requires to reach 80% or more.Control algolithm is completed by Control System Software SIMATIC PCS7 design, including AS, OS, logical Believe configuration, CFC, SFC, SCL programming and WINCC configurations etc..Segmented control method flow chart is as shown in Fig. 2, wherein (a) is square Case one:Two-part control method flow chart, (b) scheme two:Three-stage control method flow chart.
Emulation experiment is carried out according to heating, transition, each stage charge ratio of reaction, is obtained under different control methods, reactor The curve graph of temperature TI1103 (i.e. reaction rate), production concentration AI1101 (i.e. reaction conversion ratio), as shown in Figure 3,4.Compare Curve graph, it can be clearly seen that, scheme one, two is substantially better than traditional scheme in reaction rate, reaction conversion ratio.Traditional scheme Lower TI1103 rises to setting value 100 DEG C (i.e. reaction rates) and needs 510s, scheme one that 475s, scheme two is needed to need 425s; AI1101 rises to setting value 80% (i.e. reaction conversion ratio) 1008s, scheme one is needed to need 756s, scheme two under traditional scheme Need 680s;The steady-state value of AI1101 is 80.675% under traditional scheme, and scheme one, two is 83.160%;40min products are tired Accumulated amount traditional scheme is 12105.34kg, and scheme one is 13208.99kg, scheme two is 13916.90kg.
Concentration steady-state value, heating rate and the product accumulation of traditional scheme are below scheme one, two.Scheme one uses The different feeds in differential responses stage are adapted to than mode, reaction conversion ratio improves 2.485%, reaches the time contracting of set temperature Short 35s (i.e. reaction rate is accelerated), the time for reaching requirement concentration value shortens 252s, increases product accumulation.Scheme Two, transition stage is added, eliminates and changes the problem of charge proportion influences to lag on the reaction time, further improve reaction Rate increases yield.

Claims (8)

1. a kind of segmented charge ratio course control method for use based on activation energy analysis, which is characterized in that include the following steps:
1) index parameter reacted according to composite chemical in reactor, including main reaction heat release, main reaction pre-exponential factor, main reaction Activation energy, side reaction heat release, side reaction pre-exponential factor, side reaction activation energy, initial temperature, in conjunction with Arrhenius relational expressionAnalysis, it is secondary when main reaction activation energy is less than side reaction activation energy, promotes temperature quickening reaction rate The velocity coefficient of reaction increases bigger, and side reaction is easier to occur, and wherein k is reaction rate, and R is molar gas constant, and T is temperature Degree, k0And EaIt is two empirical parameters, parameter and activation energy before respectively referring to,;
2) with fixed charging ratio method emulation experiment temperature segmentation condition, division points;
3) two section type charge ratio or three-stage is used to feed ratio method;
4) Discrete control of catalyst amount is determined according to emulation experiment, it is different that adaptation is respectively configured in temperature rise period, the stage of reaction The catalyst amount in stage;
5) Chemical Manufacture model and automatic control system are established, experimental verification is carried out;
Complete the segmented charge ratio process control analyzed based on activation energy.
2. the segmented charge ratio course control method for use as described in claim 1 based on activation energy analysis, which is characterized in that institute The composite chemical reaction stated is that there are the parallel reactions of parallel competitive relation with side reaction for main reaction.
3. the segmented charge ratio course control method for use as claimed in claim 2 based on activation energy analysis, which is characterized in that institute The recombination reaction stated is more two kinds of reactants, a kind of reaction of catalyst proportion, generates principal product and by-product, wherein principal product are Purpose product.
4. the segmented charge ratio course control method for use as claimed in claim 2 based on activation energy analysis, which is characterized in that institute The indicator reaction parameter of the step 1) main reaction and side reaction stated is measured by experiment.
5. the segmented charge ratio course control method for use as claimed in claim 2 based on activation energy analysis, which is characterized in that institute Stating step 2) specific method is:After controlling certain reaction temperature and the fixed catalyst amount of input, using it is single into Material accelerates reaction process than control, and chemical reaction process reactor heats up experimental data under analysis conventional scheme, obtains difference Under temperature conditions, main reaction, side reaction reaction rate be different, determine the reaction warming-up section division points of Discrete control.
6. the segmented charge ratio course control method for use as described in claim 1 based on activation energy analysis, which is characterized in that institute The automatic control system for stating method foundation programs realization by PCS7.
7. the segmented charge ratio course control method for use as described in claim 1 based on activation energy analysis, which is characterized in that institute The technological process for stating compounded chemical reaction models in SMPT-1000 experiment porch and carries out emulation experiment verification.
8. the segmented charge ratio course control method for use as described in claim 1 based on activation energy analysis, which is characterized in that institute It is that temperature rise period charge ratio adapts to side reaction to state step 3) two section type charge ratio, and stage of reaction charge ratio adapts to main reaction hair It is raw;Three-stage charge ratio is that temperature rise period charge ratio adapts to side reaction, and the side reaction of transition stage charge ratio is to main reaction It crosses, stage of reaction charge ratio adapts to main reaction.
CN201810195109.3A 2018-03-09 2018-03-09 A kind of segmented charge ratio course control method for use based on activation energy analysis Pending CN108375905A (en)

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Application publication date: 20180807