CN112129890B - Method for accurately obtaining kinetic parameters of energetic material synthesis reaction process - Google Patents
Method for accurately obtaining kinetic parameters of energetic material synthesis reaction process Download PDFInfo
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- CN112129890B CN112129890B CN202010827592.XA CN202010827592A CN112129890B CN 112129890 B CN112129890 B CN 112129890B CN 202010827592 A CN202010827592 A CN 202010827592A CN 112129890 B CN112129890 B CN 112129890B
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- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
Abstract
The invention discloses a method for accurately obtaining kinetic parameters of an energetic material synthesis reaction process. The invention discloses a method for obtaining kinetic parameters of an energetic material synthesis reaction process, which comprises the following steps: step one, testing the heat change of the energetic material in the reaction process according to a reaction calorimetry or micro-calorimetry under an isothermal condition to obtain and record a calorimetric curve of the energetic material in the reaction process; step two, obtaining a change curve of the conversion rate along with time in the reaction process; step three, sampling at equal conversion rate time intervals to carry out concentration test; and step four, fitting a kinetic curve and obtaining kinetic parameters. Aiming at the problems in the kinetic parameter acquisition process in the energetic material synthesis reaction process, the method for accurately acquiring the kinetic parameters is provided by using the principle of conversion rate, so that the loss of an equal time interval method on important intermediate information is avoided, and the accuracy of acquiring the kinetic parameters by using concentration is improved.
Description
Technical Field
The invention belongs to the technical field of energetic materials, and mainly relates to a method for preparing an energy-containing materialSimple substanceThe reaction kinetics research of energetic material synthesis process, in particular to a method for processing kinetic parameters of energetic material synthesis reaction process with strong heat release and rapid reaction.
Background
The energetic material is a metastable substance with high energy density and can rapidly release a large amount of energy after being excited in a specific mode. The elementary substance energetic material such as energetic compound, energetic adhesive, energetic plasticizer and the like is a key base material for developing advanced explosive products, is mainly applied to various weapon systems of land, sea, air and rocket forces, is an energy material for completing launching, propelling and damaging, and is also an important energy material in national economic construction such as deep space exploration, mineral exploitation and the like.
In the synthesis reaction of the elementary substance energetic material, a large number of exothermic reactions such as nitration reaction, oxidation reaction, chlorination reaction, sulfonation reaction and the like exist, wherein the reactions such as nitration reaction, oxidation reaction and the like are mostly fast reactions with strong exotherms, the reaction process is fast and violent and is accompanied with large amount of heat release, the intermediate energy is high and poor in stability, the existence time can be vanished slightly, and the synthesis reaction process is a dynamic process taking parameters such as concentration, time, temperature and the like as variables, so that the complexity of the research on the synthesis process heat and dynamics of the energetic material is increased.
Meanwhile, the process amplification and the accurate acquisition of the thermal safety parameters are based on the thermal and kinetic parameters, so the accurate acquisition of the thermal and kinetic parameters directly influences the design of the amplification process and the acquisition of the thermal safety parameters. The current thermal effect parameters are obtained by directly testing a calibrated micro calorimeter or a reaction calorimeter; the kinetic parameters are obtained by sampling at equal time intervals in the reaction process, obtaining the reactant concentration by methods such as spectroscopy or chemical analysis and the like, and finally performing kinetic equation fitting to obtain parameters such as a reaction rate constant, a reaction order and the like.
However, for the rapid reaction with strong heat release in the energetic material synthesis process, the above kinetic parameter acquisition method has the following two problems: (1) For the rapid reaction of strong heat release, the sampling at equal time intervals can miss the rapid change process of the concentration of reactants, and the obtained kinetic parameters are not accurate enough; (2) For fast reactions where intermediates are present, important information on intermediate changes may be missed.
Disclosure of Invention
Aiming at the problems of the method for acquiring kinetic parameters of the energetic material in the synthesis reaction process, the method utilizes the result of a calorimetric curve in the reaction calorimetric process, utilizes the principle of conversion rate, and samples and researches the kinetic parameters at intervals according to the conversion rate, so that the loss of important information by an equal time interval method is avoided, and the method for accurately acquiring the kinetic parameters of the energetic material in the synthesis reaction process is provided.
In order to realize the task, the invention adopts the following technical solution:
a method for accurately obtaining kinetic parameters of an energetic material synthesis reaction process is carried out according to the following steps:
the method comprises the following steps: and testing the heat change of the energetic material in the reaction process according to a reaction calorimetry method or a micro-heating calorimetry method under an isothermal condition to obtain and record a calorimetric curve of the energetic material in the reaction process.
Randomly selecting a certain constant temperature within the temperature range of the synthesis reaction process, and testing the heat change of the energetic material in the reaction process by using a reaction calorimeter (C80 type or BT2.15 type) or a micro calorimeter (RC 1 series) to obtain and record a calorimetric curve of the energetic material in the reaction process.
Step two: the curve of the conversion rate over time during the reaction was obtained.
And (4) integrating the calorimetric curve of the energetic material in the reaction process obtained in the step one, and normalizing to finally obtain a change curve of the conversion rate of the reaction process along with time.
Step three: samples were taken at equal conversion intervals for concentration testing.
And (4) according to the conversion rate change curve obtained in the second step, carrying out synthetic reaction at the same reaction temperature, sampling at the time corresponding to the equal conversion rate interval, and testing the concentration change of main reaction materials in the reaction process by adopting a spectroscopic method or a chemical analysis method.
Step four: and fitting a kinetic curve and obtaining kinetic parameters.
The reaction formula of the energetic material synthesis reaction is assumed as follows:
A+B+…→C+D+…(1)
wherein A, B, etc. are reactants, C, D, etc. are organisms.
According to dynamic speed expression
Wherein r is the reaction rate, k is the reaction rate constant, C A 、C B Respectively the concentrations of the reactants A and B, respectively, and m and n are respectively the reaction series of the reactants A and B, respectively substituting the series of concentration data obtained in the third step into a formula (2), and fitting by adopting a least square method in Matlab software to obtain a reaction rate constant and the reaction series.
Compared with the prior art, the method for accurately obtaining the kinetic parameters of the energetic material in the synthesis reaction process has the following beneficial effects:
(1) Aiming at the rapid reaction of strong heat release in the synthesis reaction process of the energetic material, the method for accurately obtaining the kinetic parameters of the synthesis reaction process of the energetic material is provided, and the deletion of an equal time interval method on important intermediate information is avoided.
(2) By using the method, the important concentration information of each stage of the synthesis reaction can be obtained, and the accuracy of obtaining the kinetic parameters by using the concentration is improved.
(3) The method for obtaining the kinetic parameters of the energetic material in the synthesis reaction process only needs to integrate and normalize the thermal effect data, and does not increase other research work.
Drawings
FIG. 1 is a calorimetric curve and a normalized curve of the BuEA nitration reaction process.
FIG. 2 shows the regression results of the reactant concentrations in the present invention.
FIG. 3 shows the regression results of the reactant concentrations of the original method.
FIG. 4 is a graph showing the reaction amount and conversion rate in the nitrosation reaction of malononitrile.
FIG. 5 variation of the concentration of malononitrile and nitrosomalononitrile at equal conversion intervals.
Wherein
Denotes the malononitrile concentration,. Denotes the nitrosomalononitrile concentration,
represents the concentration of the malononitrile regressed concentration,
FIG. 6 comparison of concentration profiles at equal conversion intervals and at equal time intervals.
The following detailed description of the present invention is provided with reference to the accompanying drawings and examples.
Detailed Description
Example 1
The method is adopted to research the kinetic parameters of the BuEA nitration reaction process.
A BT2.15 type micro calorimeter is adopted to obtain an exothermic curve of BuEA and 98% concentrated nitric acid in the reaction process under the isothermal condition of the process temperature of 5 ℃, and the exothermic curve is shown in figure 1. The calorimetric curve of the BuEA nitration reaction process is subjected to integral treatment and normalization, and finally the change curve of the conversion rate along with time in the reaction process is obtained and is shown in figure 1.
According to the obtained conversion rate change curve, a synthetic reaction is carried out at 5 ℃, samples are taken at the time corresponding to the conversion rate interval of 0.1, infrared spectrum is drawn according to a standard curve, the concentration change of BuEA (BuEA) which is a reaction material in the reaction process is quantitatively tested, the concentration change of nitric acid in the samples is tested by an acid-base titration method, and the result is shown in table 1.
TABLE 1 concentration change of reactants during BuEA nitration reaction
The reaction formula of the BuEA nitration reaction process is as follows:
BuEA+HNO 3 →Bu－NO 2 +H 2 O (3)
the concentration data of the reactants in table 1 are respectively substituted into formula (2), fitting is performed by using the least square method in Matlab software, and the regression result is shown in fig. 2, so that the reaction rate constant and the reaction order number are obtained as follows: k =5.5541 × 10 -4 ，m＝0.92，n＝0.95。
The kinetic parameters of the energetic material synthesis reaction process of the present invention are compared with the conventional method for studying kinetic parameters at equal time intervals (sampling analysis at intervals of 3 min), and the kinetic parameters and the fitting results obtained respectively are shown in fig. 3 and table 2.
It can be seen from fig. 3 that, in the previous 4 min of the regression result of the reactant concentration of the original method, before the corresponding conversion rate is about 0.55, the regression result deviates from the actual concentration change, and the regression curve is below the actual value, so that inaccurate kinetic parameters are obtained.
As can be seen from Table 2, the method correlation coefficient of the kinetic parameters of the energetic material synthesis reaction process is 0.9936, and the standard deviation is 0.0196.
TABLE 2 comparison of kinetic parameters of the original method and the invention
Example 2
The invention is adopted to research the kinetic parameters of the malononitrile nitrosation reaction process.
Weighing 9.75g of malononitrile by using a reaction calorimeter under an isothermal condition of a process temperature of 15 ℃, adding the malononitrile into 150mL of an acetic acid aqueous solution with a mass fraction of 5%, pouring the malononitrile into a 500 mL glass reaction kettle after the malononitrile is completely dissolved, and slowly dropwise adding an aqueous solution containing 20.7g of sodium nitrite by using a feeding pump. An exotherm for the malononitrile nitrosation reaction process was obtained and is shown in figure 4. The calorimetric curve of the reaction process is integrated and normalized, and finally the change curve of the conversion rate of the reaction process along with time is obtained as shown in figure 4.
According to the obtained conversion rate change curve, the synthesis reaction was carried out at 15 ℃, and sampling was carried out at a time corresponding to a conversion rate interval of 0.1, and the change in the concentration of malononitrile and nitromalononitrile, which were reaction materials in the reaction process, was quantitatively measured by infrared spectroscopy according to a plotted standard curve, with the results shown in table 3.
TABLE 3 variation of the concentration of malononitrile and nitrosomalononitrile
The reaction formula of the malononitrile nitrosation reaction process is as follows:
malononitrile + sodium nitrite → nitrosomalononitrile + sodium hydroxide → diformyloxymalononitrile (4)
The concentration data of the reactants in table 3 are respectively substituted into formula (2), fitting is performed by using the least square method in Matlab software, and the regression result is shown in fig. 5, and the reaction rate constant and the reaction order number are obtained as follows: k =2.3194 × 10 -2 ，m＝2.00，n＝1.00。
The method for kinetic parameters of energetic material synthesis reaction process of the present invention is compared with the general method for researching kinetic parameters at equal time intervals (sampling analysis at intervals of 200 s), and the kinetic parameters and the fitting results obtained respectively are shown in fig. 6 and table 4.
As can be seen from FIG. 6, the regression result of reactant concentration of the original method is within 0.1-0.7 of conversion rate and the corresponding time is about 200-1000 s, only 3 concentration points fit the reaction kinetics when the concentration of the intermediate product has a peak value, while the method provided by the invention has 7 concentration points to fit the reaction kinetics in the interval, and the fitting accuracy is greatly improved (R is a value of the concentration point in the interval) 2 =0.9985, standard deviation of 1.60 × 10 -4 ) The specific parameters are shown in Table 4.
As can be seen from Table 4, the process correlation coefficient for kinetic parameters of the energetic material synthesis reaction process of the present invention is 0.9985 with a standard deviation of 1.60X 10 -4 It is apparent that the inventionThe accuracy of the method for acquiring kinetic parameters in the synthesis reaction process of the energetic material is greatly improved.
TABLE 4 comparison of kinetic parameters of the original method and the invention
Claims (1)
1. A method for accurately obtaining kinetic parameters of an energetic material synthesis reaction process is characterized by comprising the following steps:
the method comprises the following steps: under the isothermal condition, testing the heat change of the energetic material in the reaction process according to a reaction calorimetry method or a micro-heating calorimetry method to obtain and record a calorimetric curve of the energetic material in the reaction process;
step two: obtaining a change curve of the conversion rate of the reaction process along with time, namely performing integral treatment on the calorimetric curve of the energetic material obtained in the step one in the reaction process, and normalizing to finally obtain a change curve of the conversion rate of the reaction process along with time;
step three: sampling at equal conversion intervals for concentration testing:
according to the conversion rate change curve obtained in the second step, carrying out synthesis reaction at the same reaction temperature, sampling at the time corresponding to the equal conversion rate interval, and testing the concentration change of main reaction materials in the reaction process;
step four: fitting a kinetic curve and obtaining kinetic parameters:
the reaction formula of the energetic material synthesis reaction is assumed as follows:
A+B+…→C+D+… (1)
wherein A and B are reactants, C and D are creatures;
according to dynamic speed expression
Wherein r is the reaction rate, k is the reaction rate constant, C A 、C B And (3) respectively representing the concentrations of the reactants A and B, and m and n respectively representing the reaction stages of the reactants A and B, respectively substituting the series of concentration data obtained in the step three into a formula (2), and fitting by adopting a least square method to obtain a reaction rate constant and the reaction stages.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61233651A (en) * | 1985-04-08 | 1986-10-17 | Nippon Ester Co Ltd | Production of glycol ester of terephthalic acid |
| CN1916605A (en) * | 2006-08-31 | 2007-02-21 | 山东省科学院海洋仪器仪表研究所 | Method for analyzing kinetic parameters of ozone oxidation reaction through dynamics curve of chemiluminescence |
| CN105548237A (en) * | 2015-12-15 | 2016-05-04 | 中国人民解放军第二炮兵工程大学 | Method for building energetic material mesoscopic hot spot physical model |
| CN105675797A (en) * | 2016-02-03 | 2016-06-15 | 广西大学 | Method for measuring kinetic parameters of enzyme catalyzed reaction through isothermal titer thermal method |
| CN109470738A (en) * | 2018-12-12 | 2019-03-15 | 西安近代化学研究所 | Micro-calorimetry quantitative assessment double-base propellant thermal stability |
| CN110531026A (en) * | 2019-08-30 | 2019-12-03 | 西安建筑科技大学 | A method of measurement powder material suspended state kinetics |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2007012239A (en) * | 2005-04-01 | 2007-12-07 | Monsanto Technology Llc | Control of n-(phosphonomethyl) iminodiacetic acid conversion in manufacture of glyphosate. |
-
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- 2020-08-17 CN CN202010827592.XA patent/CN112129890B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61233651A (en) * | 1985-04-08 | 1986-10-17 | Nippon Ester Co Ltd | Production of glycol ester of terephthalic acid |
| CN1916605A (en) * | 2006-08-31 | 2007-02-21 | 山东省科学院海洋仪器仪表研究所 | Method for analyzing kinetic parameters of ozone oxidation reaction through dynamics curve of chemiluminescence |
| CN105548237A (en) * | 2015-12-15 | 2016-05-04 | 中国人民解放军第二炮兵工程大学 | Method for building energetic material mesoscopic hot spot physical model |
| CN105675797A (en) * | 2016-02-03 | 2016-06-15 | 广西大学 | Method for measuring kinetic parameters of enzyme catalyzed reaction through isothermal titer thermal method |
| CN109470738A (en) * | 2018-12-12 | 2019-03-15 | 西安近代化学研究所 | Micro-calorimetry quantitative assessment double-base propellant thermal stability |
| CN110531026A (en) * | 2019-08-30 | 2019-12-03 | 西安建筑科技大学 | A method of measurement powder material suspended state kinetics |
Non-Patent Citations (3)
| Title |
|---|
| DNBP的合成及动力学研究;张龙等;《化工科技》;20000831;第8卷(第4期);13-17 * |
| 新方法研究变温反应DOTP合成的动力学;李科;《化学工程师》;20130725;第27卷(第07期);1-3+7 * |
| 等温滴定量热法测定脲酶催化尿素水解反应动力学;宋熙熙等;《浙江大学学报(理学版)》;20090331;第36卷(第02期);175-179 * |
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