CN112102892B - Method for determining temperature correction coefficient of energetic material combination process - Google Patents
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- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
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- AHLHDIKRENEJHF-UHFFFAOYSA-N n-ethylnitramide Chemical compound CCN[N+]([O-])=O AHLHDIKRENEJHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for determining a temperature correction coefficient of an energetic material combining process, which comprises the steps of obtaining thermal decomposition reaction kinetic parameters according to material thermal decomposition characteristic quantity of an energetic material in a combining process, further obtaining process temperatures required by maximum reaction rate reaching time under different dangerous grade adiabatic conditions, and quantitatively obtaining a temperature correction coefficient gamma by taking the process temperatures of different dangerous grades and specific operation time as scales 1 . The method disclosed by the invention has universality, is suitable for evaluating the thermal stability of materials of different energetic materials, is comprehensive and reliable in determination of the temperature correction coefficient, strong in operability, conservative in result of the determined temperature correction coefficient, and high in safe use reliability.
Description
Technical Field
The invention belongs to the technical field of energetic material risk assessment, and mainly relates to a method for determining a temperature correction coefficient of an energetic material compounding process.
Background
The energetic material has the characteristic of easy combustion and explosion under the stimulation of heat, static electricity, machinery and the like, and the development of combustion and explosion risk assessment in the process of compounding the energetic material is an important content of safe production design and management and control. The material in the energy-containing material compounding process is a heat bad conductor and is extremely sensitive to heat stimulus, the self-catalytic decomposition exothermic reaction can be generated after heating, and the heat accumulation is extremely easy to generate to cause thermal explosion, so that the heat explosion is a inducing factor of a large number of safety accidents, and the combustion explosion risk evaluation in the process firstly needs to quantitatively determine the temperature correction coefficient in the process. The invention quantitatively determines the temperature correction coefficient in the chemical combination process aiming at the energetic material.
In order to qualitatively understand and quantitatively estimate the risk of combustion and explosion, quantitative evaluation methods (BZA for short) of important hazard sources of explosive and product enterprises are prepared in China according to the characteristics of the explosive and explosive enterprises and by referring to foreign evaluation experience -1 A method of. BZA (binary arithmetic coding) -1 The dangerous source assessment mathematical model and the physical meaning proposed by the method are as follows:
H＝H inner part +H Outer part (1)
Wherein: h is the actual risk of the explosion hazard source system, H Inner part To be the actual dangerous degree in the system, H Outer part Is the real risk degree outside the system.
Wherein H is Inner part The calculation method of (2) is as follows:
H inner part ＝V+KB (2)
Wherein: v is a substance risk coefficient, namely the inherent static risk of the explosive, K is a controlled degree coefficient of controllable dangerous behavior in the system, and B is the controllable risk in the system.
The controllable risk B in the system is calculated by the following formula:
B＝W B ·D·P (3)
wherein: w (W) B The energy risk coefficient of the materials of the explosive and the device is calculated by the following formula.
W B ＝V·γ (4)
Wherein, gamma is a process risk coefficient, and the calculation formula is as follows:
γ＝γ 1 +γ 2 +γ 3 +γ 4 +γ 5 (5)
wherein: gamma ray 1 Is a temperature correction coefficient, and has positive correlation with the temperature rise, gamma 2 For the chemical medium correction factor, gamma 3 For correction coefficient of drug delivery, gamma 4 Correction of coefficients for other mechanical action (e.g. cutting, drilling, sawing, rubbing, etc.), gamma 5 Is an electrostatic correction coefficient.
Temperature correction coefficient gamma in the current process 1 The values were as follows (see Table 1)
TABLE 1 dangerous coefficient gamma value condition in process
As can be seen from Table 1, the temperature correction coefficient γ 1 The determination method of the method is a semi-quantitative method, although the corresponding evaluation parameters are adopted, the actual operability is poor, the values cannot be accurately quantized one by one, the concept meaning of the value condition is not clear, the quantitative criterion is lacking, and the dangerous degree of the materials in the process is difficult to evaluate by effectively combining with the actual process condition.
Because the material in the process of compounding the energetic material is an energetic material, a combustion explosion accident can be caused by decomposition exothermic reaction under the action of heat, so that whether the material can keep stable after being stimulated by process temperature in the process is one of important indexes of process dangers, accurate evaluation of thermal stability is an important way for realizing intrinsic process safety, and scientific basis is provided for quantitative evaluation of dangers, formulation of early warning and prevention and control measures of the whole process production line, so that a determination method of a temperature correction coefficient in the process of compounding the energetic material is urgently needed.
Disclosure of Invention
For the existing temperature correction coefficient gamma 1 The invention provides a method for determining the value of a temperature correction coefficient gamma 1 In order to realize the task, the invention adopts the following technical scheme:
a method for determining the temperature correction coefficient of the combination process of an energetic material is characterized in that a differential scanning calorimetry is used for testing the thermal decomposition reaction of the material to obtain the apparent activation energy E of kinetic parameters a And factor A before finger, thereby obtaining thermal insulation with different dangerous gradesProcess temperature T required for the arrival time of the conditional maximum reaction rate p And process temperatures T at different hazard classes p And comparing and measuring the actual process temperature T of the materials in the process by taking the specific operation time coefficient delta as a scale ps Actual process temperature time t s Quantitatively acquiring a temperature correction coefficient gamma 1 . The flow chart of determining the temperature correction coefficient is shown in fig. 1, and specifically comprises the following steps:
step one: differential scanning calorimetric test for obtaining apparent activation energy E of material thermal decomposition reaction kinetic parameter in energetic material chemical combination process a And pre-finger factor a.
The thermal decomposition reaction of the material in the process of compounding the energetic material is obtained by utilizing a differential scanning calorimetric test, the exothermic reaction peak temperature which causes the rapid decomposition of the material is obtained, and the kinetic parameter apparent activation energy E of the thermal decomposition reaction of the material is obtained by utilizing the regression of a Kissinger equation formula (1) a And factor a before finger:
wherein beta is i K/s is the temperature rising rate; t is the peak temperature of decomposition, K; a is a pre-finger factor, s -1 ；E a J/mol is apparent activation energy; r is the gas constant, J/(mol.K). From the following components
For->
Drawing to obtain a straight line, and calculating E from the slope of the straight line a A is found from the intercept.
Step two: obtaining different hazard classes adiabatic conditions maximum reaction rate arrival time TMR ad Required process temperature T p 。
TMR ad The calculation formula of (2) is shown as the following formula (II):
wherein E is a J/mol is the activation energy; a is a pre-finger factor, s -1 ；T p Is the process temperature, K; r is a gas constant, J/(mol.K); c p J/(g.K) is the specific heat capacity of the material; q (Q) r J/g is the exothermic amount of thermal decomposition of materials.
TMR using 6-level criteria as decision criteria by the Zurich Hazard Analysis ad 100h,50h,24h,12h,8h,1h, respectively, up to 6 TMR were obtained from equation (II) ad Required process temperature T p The method sequentially comprises the following steps: t (T) D100 、T D50 、T D24 、T D12 、T D8 、T D1 。
Step three: maximum reaction rate arrival time TMR of 6 adiabatic conditions at different hazard classes ad Dividing the process temperature T p At a process temperature T p The actual process temperature T of the material is compared and measured by using the scale ps Quantitatively obtaining a temperature correction coefficient gamma 1 。
Due to TMR ad Process temperature T required for =100 h p Is T D100 Thus, for TMR ad Not less than 100h, when the actual process temperature T of the material ps ≤T D100 At the time, the temperature correction coefficient gamma 1 ＝1；
Due to TMR ad Process temperature T required for =50h p Is T D50 Thus, for 50 h.ltoreq.TMR ad Less than 100h, when the actual process temperature T of the material D100 ＜T ps ≤T D50 At the time, the temperature correction coefficient gamma 1 ＝2；
Due to TMR ad Process temperature T required for 24h p Is T D24 Thus, for 24 h. Ltoreq.TMR ad Less than 50 hours when the actual process temperature T of the material D50 ≤T ps ＜T D24 At the time, the temperature correction coefficient gamma 1 ＝3；
Due to TMR ad Process temperature T required for 12h p Is T D12 Thus, for 12 h. Ltoreq.TMR ad For less than 24 hours, when the actual process temperature T of the material D24 ＜T ps ≤T D12 At the time, the temperature correction coefficient gamma 1 ＝4；
Due to TMR ad Process temperature T required for =8h p Is T D8 Thus, for 8 h. Ltoreq.TMR ad For less than 12 hours, when the actual process temperature T of the material D12 ＜T ps ≤T D8 At the time, the temperature correction coefficient gamma 1 ＝5；
Due to TMR ad Process temperature T required for =1h p Is T D1 Thus:
for 1 h.ltoreq.TMR ad For less than 8 hours, when the actual process temperature T of the material D8 ＜T ps ≤T D1 At the time, the temperature correction coefficient gamma 1 ＝6～9；
For TMR ad Not more than 1h, when the actual process temperature T of the material ps ≥T D1 At the time, the temperature correction coefficient gamma 1 ＝10。
Temperature correction coefficient gamma 1 The determination of (2) is shown in table 2:
table 2 temperature correction coefficient values
Step four: temperature correction coefficient gamma 1 When the value range is 6-9, namely the actual process temperature T D8 ≤T ps ＜T D1 When the temperature correction coefficient gamma is obtained by taking the specific operation time coefficient delta of different dangerous grades as a scale, the temperature correction coefficient gamma is obtained further quantitatively 1 。
γ 1 When the value range is 6-9, TMR is utilized ad Further determining the operation time in the actual technological process of the materials, and calculating a specific operation time coefficient delta according to a formula (III):
wherein: TMR (TMR) ad The maximum reaction rate reaching time, h, of the adiabatic condition at the process temperature; t is the operation time of the material in the process, h. The physical meaning of the specific operation time coefficient is the safety margin of the operation time of the process, when gamma 1 At 6 to 9, the temperature correction coefficient, gamma, is determined based on a safety margin of 1.5 times, 2 times, 4 times, i.e. the specific operation time coefficient delta=1, delta=2.5, delta=4 1 The determination schemes at 6 to 9 are shown in Table 3.
TABLE 3 temperature correction coefficient gamma 1 Scheme for taking value at 6-9
Compared with the prior art, the method for determining the temperature correction coefficient of the energetic material combining process has the following beneficial effects:
(1) The temperature correction coefficient gamma of the invention 1 The process temperature of different dangerous grades is used as a measuring scale, the process temperature is obtained by thermal decomposition kinetic parameters based on the intrinsic thermal decomposition characteristics of the materials in the process of compounding the energetic materials, and the process conditions are combined to reflect the material properties of different process production lines, so that the method has universality and is suitable for evaluating the thermal stability of the materials of different energetic materials;
(2) The temperature correction coefficient gamma of the invention 1 The process and the specific operation time coefficient required by the maximum reaction rate reaching time of the adiabatic conditions of different dangerous grades are used as the scale in the determination within the range of 6-9, wherein the specific operation time coefficient scale is determined based on the safety margin of the process operation time, and the actual process temperature and the actual operation time are compared for evaluation, so that the determination of the temperature correction coefficient is comprehensive and reliable, and the operability is strong;
(3) Quantitatively determining a temperature correction coefficient gamma 1 The method provides scientific basis for quantitatively evaluating the dangers, making early warning and prevention and control measures of the whole process production line;
(4) The invention adopts the maximum reaction rate reaching time TMR under the adiabatic condition ad Determining a temperature correction coefficient based on the corresponding temperatureγ 1 The heat generated by the decomposition reaction of the materials under the adiabatic condition is not lost, and is the most severe condition, so that the temperature obtained under the adiabatic condition is the most conservative temperature, the result of the determined temperature correction coefficient is conservative, and the safety and the reliability of use are high.
Drawings
FIG. 1 shows a temperature correction coefficient gamma of the present invention 1 A value scheme flow of (1);
fig. 2 is a DSC profile of the temperature ramp rates β=2.5, 5, 10, 20 ℃/min for the examples of the present invention;
FIG. 3 kinetic parameters of the thermal decomposition reaction of BuNENA material according to the example of the invention.
Detailed Description
The invention relates to a method for determining a temperature correction coefficient of an energetic material compounding process, which takes a material BuNENA of a butyl nitroxide ethyl nitroamine compounding process as a research object, adopts a differential scanning calorimetry method to test material thermal decomposition reaction, obtains thermal decomposition characteristic quantities at different heating rates, and obtains kinetic parameter apparent activation energy E of the material thermal decomposition reaction according to Kissinger equation regression a And pre-finger factor A, thereby obtaining TMR between reaching maximum reaction rates of different dangerous grade adiabatic conditions ad Required process temperature T p And process temperatures T at different hazard classes p And comparing and measuring the actual process temperature T of the materials in the process by taking the specific operation time coefficient delta as a scale ps Actual process temperature time t s Quantitatively acquiring a temperature correction coefficient gamma 1 . The process is carried out by referring to FIG. 1, specifically, the following steps are carried out:
step one: differential scanning calorimetric test for obtaining apparent activation energy E of material thermal decomposition reaction kinetic parameter in BuNENA chemical combination process a And pre-finger factor a.
Carrying out Differential Scanning Calorimeter (DSC) thermal test, and respectively carrying out temperature programming test material thermal decomposition reaction at the temperature rise rates of beta=2.5, 5, 10 and 20 ℃/min to obtain thermal decomposition curves as shown in fig. 2, wherein the material has two exothermic peaks in the thermal decomposition process, and the first decomposition heat release of the material causes the subsequent rapid material decomposition reaction to cause the subsequent rapid heat release, so that the kinetic parameters are calculated according to the first exothermic peak-to-peak temperature, the thermal decomposition curves are shown in fig. 2, and the obtained thermal decomposition peak temperatures are shown in table 4:
TABLE 4BuNENA material thermal decomposition parameters at different heating rates
Obtaining kinetic parameter apparent activation energy E of thermal decomposition reaction of materials by regression of Kissinger equation formula (I) a And factor a before finger:
wherein beta is i Is the temperature rising rate, and is at the temperature of DEG C/s; t is the peak temperature (absolute temperature) of decomposition and K is the peak temperature of the decomposition; a is a pre-finger factor, s -1 ；E a J/mol is apparent activation energy; r is the gas constant, J/(mol.K). From the following components
For->
Drawing to obtain a straight line, and obtaining apparent activation energy E from the slope of the straight line as shown in FIG. 3 a 118.60kJ/mol, pre-finger factor a=e from intercept 24.50 s -1 。
Step two: obtaining different hazard classes adiabatic conditions maximum reaction rate arrival time TMR ad Required process temperature T p 。
TMR ad The calculation formula of (2) is shown as the following formula (II):
wherein E is a J/mol is the activation energy; a is a pre-finger factor, s -1 The method comprises the steps of carrying out a first treatment on the surface of the T is the process temperature, K; r is a gas constant, J/(mol.K); c p J/(g.K) is the specific heat capacity of the material; q (Q) r J/g is the exothermic amount of thermal decomposition of materials.
Apparent activation energy E a 118.60kJ/mol, pre-finger factor a=e 24.50 s -1 Gas constant R= 8.314J/mol.g, specific heat capacity c of the material p Heat release amount Q of thermal decomposition of material =2j/(g·k) r =2182J/g is brought into formula (ii), calculated to obtain TMR at 6 likelihood levels ad The process temperatures T required for 100h,50h,24h,12h,8h and 1h respectively D100 、T D50 、T D24 、T D12 、T D8 、T D1 。
TMR ad Process temperature T required for =100 h p Is T D100 ＝64.6℃，
TMR ad Process temperature T required for =50h p Is T D50 ＝70.6℃，
TMR ad Process temperature T required for 24h p Is T D24 ＝77.1℃，
TMR ad Process temperature T required for 12h p Is T D12 ＝83.5℃，
TMR ad Process temperature T required for =8h p Is T D8 ＝87.3℃，
TMR ad Process temperature T required for =1h p Is T D1 ＝108.4℃。
Step three: maximum reaction rate arrival time TMR of 6 adiabatic conditions at different hazard classes ad Dividing the process temperature T p At a process temperature T p The actual process temperature T of the material is compared and measured by using the scale ps Quantitatively obtaining a temperature correction coefficient gamma 1 。
Due to TMR ad Process temperature T required for =100 h p Is T D100 Thus, for TMR ad Not less than 100h, when the actual process temperature T of the material ps ≤T D100 When, i.e. T ps <Temperature correction coefficient gamma of 64.6 DEG C 1 ＝1；
Due to TMR ad Process temperature T required for =50h p Is T D50 Thus, for 50 h.ltoreq.TMR ad Less than 100h, when the actual process temperature T of the material D100 ＜T ps ≤T D50 When, i.e. 64.6.ltoreq.T ps A temperature correction coefficient gamma of < 70.6 1 ＝2；
Due to TMR ad Process temperature T required for 24h p Is T D24 Thus, for 24 h. Ltoreq.TMR ad Less than 50 hours when the actual process temperature T of the material D50 ≤T ps ＜T D24 When, i.e. 64.6.ltoreq.T ps Temperature correction coefficient gamma of < 77.1 1 ＝3；
Due to TMR ad Process temperature T required for 12h p Is T D12 Thus, for 12 h. Ltoreq.TMR ad For less than 24 hours, when the actual process temperature T of the material D24 ＜T ps ≤T D12 When, i.e. 77.1.ltoreq.T ps A temperature correction coefficient gamma of < 83.5 1 ＝4；
Due to TMR ad Process temperature T required for =8h p Is T D8 Thus, for 8 h. Ltoreq.TMR ad For less than 12 hours, when the actual process temperature T of the material D12 ＜T ps ≤T D8 When, i.e. 83.5.ltoreq.T ps A temperature correction coefficient gamma of < 87.3 1 ＝5；
Due to TMR ad Process temperature T required for =1h p Is T D1 Thus:
for 1 h.ltoreq.TMR ad For less than 8 hours, when the actual process temperature T of the material D8 ＜T ps ≤T D1 When T is 87.3 ∈ ps Temperature correction coefficient gamma of < 108.4 1 ＝6～9；
For TMR ad Not more than 1h, when the actual process temperature T of the material ps ≥T D1 T, i.e ps >Temperature correction coefficient gamma of 108.4 DEG C 1 ＝10；
Step four: temperature correction coefficient gamma 1 When the value range is 6-9, namely the actual process temperature T D8 ≤T ps ＜T D1 At the same time, at different hazard level ratiosThe operation time coefficient delta is used as a scale, and the temperature correction coefficient gamma is further quantitatively obtained 1 。
γ 1 When the value is 6-9, TMR is utilized ad Further determining the operation time t of the actual material in the process, wherein the calculation formula (III) of the ratio operation time coefficient delta is shown as follows:
wherein: TMR (TMR) ad The maximum reaction rate reaching time under the adiabatic condition process temperature is h; t is the operation time of the material in the process, h. The physical meaning of the specific operation time coefficient is the safety margin of the operation time of the process, when gamma 1 At 6-9, the temperature correction coefficient, gamma, is divided based on 1.5 times, 2 times, 4 times safety margin, i.e. the specific operation time coefficient delta=1, delta=2.5, delta=4 1 The determination schemes at 6 to 9 are shown in Table 3:
TABLE 3 temperature correction coefficient gamma 1 Values at 6-9
Based on the above results, the determination of the temperature correction coefficient of BuNENA material in the process of butyl nitroxide ethyl nitroamine is shown in Table 4
Table 4 temperature correction coefficient values for BuNENA synthesis process
The actual process temperature of the materials in the process of synthesizing the butyl nitroxide ethyl nitramine is 35 ℃, so according to the division of the temperature dangerous grade, the temperature correction coefficient gamma of the materials under the process condition 1 ＝1。
Claims (1)
1. A method for determining a temperature correction coefficient of an energetic material compounding process, the method comprising the steps of:
step one: differential scanning calorimetric test for obtaining apparent activation energy E of material thermal decomposition reaction kinetic parameter in energetic material chemical combination process a And factor a before finger:
the thermal decomposition reaction of the material in the process of compounding the energetic material is obtained by utilizing a differential scanning calorimetric test, the exothermic reaction peak temperature which causes the rapid decomposition of the material is obtained, and the kinetic parameter apparent activation energy E of the thermal decomposition reaction of the material is obtained by utilizing Kissinger equation formula (I) regression a And factor a before finger:
wherein beta is i K/s is the temperature rising rate; t is the peak temperature of decomposition, K; a is a pre-finger factor, s -1 ；E a J/mol is apparent activation energy; r is a gas constant, J/(mol.K);
step two: obtaining different hazard classes adiabatic conditions maximum reaction rate arrival time TMR ad Required process temperature T p ；
TMR ad The calculation formula of (2) is shown as the following formula (II):
wherein E is a J/mol is apparent activation energy; a is a pre-finger factor, s -1 ；T p Is the process temperature, K; r is a gas constant, J/(mol.K); c p J/(g.K) is the specific heat capacity of the material; q (Q) r J/g is the heat release amount of thermal decomposition of materials;
TMR using 6-level criterion of Zuishi risk analysis as determination condition ad 100h,50h,24h,12h,8h,1h, respectively, up to 6 TMR were obtained from equation (II) ad Required process temperature T p The method sequentially comprises the following steps: t (T) D100 、T D50 、T D24 、T D12 、T D8 、T D1 ；
Step three: maximum reaction rate arrival time TMR of 6 different hazard classes under adiabatic conditions of different hazard classes ad Dividing the process temperature T p At a process temperature T p The actual process temperature T of the material is compared and measured by using the scale ps Quantitatively obtaining a temperature correction coefficient gamma 1 The method comprises the following steps:
step four: temperature correction coefficient gamma 1 The value range is 6-9, namely the actual process temperature T D8 ≤T ps ＜T D1 When the temperature correction coefficient gamma is obtained by taking the specific operation time coefficient delta of different dangerous grades as a scale, the temperature correction coefficient gamma is obtained further quantitatively 1 ：
γ 1 When the value range is 6-9, TMR is utilized ad Further determining the operation time in the actual technological process of the materials, and calculating a specific operation time coefficient delta according to a formula (III):
wherein: TMR (TMR) ad The maximum reaction rate reaching time under the adiabatic condition, and t is the operation time of the material in the process; the specific operation time coefficient is the safety margin of the operation time of the process, and when gamma is 1 At 6-9, the temperature correction coefficient of the material, namely gamma, is determined based on the safety margin of 1.5 times, 2 times and 4 times, namely the specific operation time coefficient delta=1, delta=2.5 and delta=4 1 Temperature correction coefficient gamma at 6-9 1 The method comprises the following steps:
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