Method and system for rapidly obtaining risk control important parameter TMR and storage medium

Abstract

The invention discloses a method and a system for quickly acquiring a risk control important parameter TMR and a storage medium, and relates to the field of risk assessment and risk control in a chemical process. The method comprises the following steps: obtaining thermal decomposition characteristics of a target material at different temperatures through an adiabatic heat test; determining that the thermal decomposition behavior of the target material is not detected on a set detection line based on the thermal decomposition characteristics; and predicting TDx according to the adiabatic tracking time and the tracking temperature, obtaining a TMRad value range at a certain temperature after obtaining a TDx value range, and completing related reaction safety risk assessment and risk control. According to the technical scheme, the numerical range of the TMRad and the TDx of the material is given.

Description

Technical Field

[0001] The present invention relates to the field of risk assessment and risk control of chemical process, and more specifically to a method for rapidly acquiring an important risk control parameter TMR. Background Art

[0002] The time to reach the maximum reaction rate (TMR ad ) is an important parameter for thermal risk assessment and control of chemical processes. The national standard GB / T 42300, Specification for Safety Risk Assessment of Fine Chemical Reactions, proposes TMR ad The specific acquisition method is usually to obtain the thermal decomposition characteristic data of the material by testing the thermal stability of the material in the chemical reaction endpoint system, further carry out the decomposition kinetics research, select the corresponding N-level, autocatalytic or multi-stage decomposition kinetic models to carry out research, and obtain the maximum reaction rate arrival time TMR under adiabatic conditions. ad The value and the temperature T corresponding to the maximum reaction rate reaching time xh Dx The method described in this patent can quickly determine the TMR through a set of adiabatic calorimetry tests. ad Numerical range, to solve the problem that the material within the limited test range is not decomposed and T cannot be obtained Dx This method is not limited by the upper temperature limit of the instrument, has low experimental workload, high efficiency, and can quickly obtain the TMR of the specified material. ad and T Dx The numerical range is used to complete the response safety risk assessment and risk control needs.

[0003] In the existing patent, a chemical reaction risk analysis method (CN115273998B) obtains the safety data and preventive measures of the reaction by analyzing the material stability, reaction process risk and loss of control in the chemical reaction. The patent proposes a method for quickly obtaining TMR. ad and T Dx The experimental test method is proposed, but no relevant calculation method is proposed. At present, no TMR of decomposed materials within the test range is found in the existing literature and patents. ad and T Dx Ways to obtain it. Summary of the invention

[0004] In view of this, the present invention provides a method for quickly obtaining the important risk control parameter TMR, which gives the material TMR ad and T Dx The numerical range of .

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] A method for quickly obtaining the important risk control parameter TMR comprises the following steps:

[0007] Obtain the thermal decomposition characteristics of the target material at different temperatures through adiabatic calorimetry testing;

[0008] Determining based on the thermal decomposition characteristics that no thermal decomposition behavior of the target material is detected at the set detection line;

[0009] Predict T based on adiabatic tracking time and tracking temperature Dx , get T Dx After the value range is set, the TMR at a certain temperature can be obtained. ad Numerical range, complete relevant reaction safety risk assessment and risk control.

[0010] Optionally, predict T based on adiabatic tracking time and tracking temperature Dx , the expression is as follows:

[0011]

[0012] Where, T Dx It represents the temperature corresponding to the maximum reaction rate reaching time x hours under adiabatic conditions; T z Indicates the upper limit temperature of adiabatic tracking without decomposition; t z Indicates the upper limit time for adiabatic tracking to not decompose.

[0013] Optionally, the target material undergoes a reaction, and the reaction kinetics equation is as follows:

[0014]

[0015] Where r j represents the reaction rate, k j represents the reaction rate constant; C i represents the concentration of component i in the reaction system; m i represents the reaction order of component i.

[0016] Optionally, the reaction rate constant k j Expressed as:

[0017] Optionally, the concentration of component i in the reaction system is expressed as:

[0018]

[0019] Where N i represents the number of moles of component i, m r Indicates the quality of the reaction system.

[0020] Optionally, the generation rate R of component i in the reaction system iExpressed as:

[0021]

[0022] In the formula, R i represents the generation rate of component i in reaction j; v ij represents the stoichiometric number of component i in reaction j; m r Indicates the quality of the reaction system.

[0023] Optionally, relate the reaction thermodynamics to the reaction kinetics, the reaction power q rx,j Expressed as:

[0024]

[0025] Where q rx,j Represents the reaction power; r H j Represents specific reaction heat; M i Indicates molar mass; m i represents the reaction order of component i.

[0026] A system for quickly obtaining the important risk control parameter TMR includes the following steps:

[0027] Thermal decomposition characteristics acquisition module: used to obtain the thermal decomposition characteristics of the target material at different temperatures through adiabatic calorimetry;

[0028] Thermal decomposition behavior occurrence judgment module: used to determine, based on thermal decomposition characteristics, that no thermal decomposition behavior of the target material is detected at a set detection line;

[0029] Risk assessment and control module: used to predict T based on adiabatic tracking time and tracking temperature Dx , get T Dx After the value range is set, the TMR at a certain temperature can be obtained. ad Numerical range, complete relevant reaction safety risk assessment and risk control.

[0030] A computer storage medium having a computer program stored thereon, wherein when the computer program is executed by a processor, the steps of any one of the methods for quickly obtaining an important risk control parameter TMR are implemented.

[0031] It can be seen from the above technical solution that, compared with the prior art, the present invention provides a method for quickly obtaining the important risk control parameter TMR, which can quickly obtain TMR through a short-term adiabatic thermal test. ad and T Dx , solve the problem that the material within the limited test range is not decomposed and T cannot be obtained DxThe problem of numerical value is that this method is not limited by the upper temperature limit of the instrument and equipment. The corresponding results can be applied to the reaction safety risk assessment, complete the possibility of runaway reaction, the acceptability of runaway reaction and the hazard of reaction process, obtain the corresponding risk assessment level, and according to TMR ad and T Dx Propose risk control temperature points. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0033] Figure 1 It is a schematic diagram of the method flow of the present invention;

[0034] Figure 2 It is a schematic diagram of the system structure of the present invention;

[0035] Figure 3 It is a time-temperature-pressure curve diagram of adiabatic calorimetry test of materials in the end point system of acetic anhydride hydrolysis reaction;

[0036] Figure 4 This is a diagram of adiabatic calorimetry and constant temperature testing of materials in the endpoint system of acetic anhydride hydrolysis reaction;

[0037] Figure 5 It is a time-temperature-pressure curve diagram of 5% tert-butyl hydroperoxide adiabatic accelerated calorimetry test;

[0038] Figure 6 5% tert-butyl hydroperoxide decomposition reaction TMR ad Graphs;

[0039] Figure 7 This is a diagram of a 5% tert-butyl hydroperoxide adiabatic thermal constant temperature test. DETAILED DESCRIPTION

[0040] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] Example 1

[0042] The embodiment of the present invention discloses a method for quickly obtaining the important risk control parameter TMR, such as Figure 1 As shown, the following steps are included:

[0043] Step 1: Obtain the thermal stability data of the material at a certain temperature and for a certain time through an adiabatic calorimetric test;

[0044] Step 2: Find the tracking time corresponding to different adiabatic calorimetry test temperatures as needed;

[0045] Step 3: Predict T based on adiabatic tracking time and tracking temperature Dx , get T Dx After the value range is set, the TMR at a certain temperature can be obtained. ad Numerical range, complete relevant reaction safety risk assessment and risk control.

[0046] Specifically, the fine chemical industry involves a large number of chemical materials (raw materials, intermediates, products, waste, etc.). Usually, the thermal decomposition characteristics of materials at different temperatures are obtained through adiabatic calorimetry, and then the TMR is calculated through the appropriate model. ad and T Dx , complete the assessment of the possibility of runaway reaction, the acceptability of runaway reaction and the hazard level of reaction process, obtain the corresponding risk assessment level, and propose the risk control temperature point.

[0047] Assuming that j reactions occur in the system, the reaction kinetics equation is shown in equation (1):

[0048]

[0049] Where r j —Reaction rate, in mol kg -1 ·s -1 ;k j —reaction rate constant; C i —The concentration of component i in the reaction system, in mol kg -1 ;m i —Reaction order of component i.

[0050] Reaction rate constant k j It can be expressed as formula (2):

[0051]

[0052] The concentration of component i in the reaction system can be expressed as (3):

[0053]

[0054] Where N i —The number of moles of component i, in mol; m r —Mass of reaction system, in kg.

[0055] The generation rate R of component i in the reaction system i It is expressed as formula (4):

[0056]

[0057] Where R i —The rate at which component i is generated in reaction j, in mol kg -1 ·s -1 ;v ij —The stoichiometric number of component i in reaction j, in mol; m r —Mass of reaction system, in kg.

[0058] In any chemical reaction, the process of converting raw materials into intermediates and products will involve energy conversion. By correlating reaction thermodynamics with reaction kinetics, the reaction power q rx,j It is expressed as formula (5):

[0059]

[0060] Where q rx,j —reaction power, unit is w; r H j —Specific reaction heat, in J·g -1 ;M i —Molar mass, in kg·mol 1 ;m i —The reaction order of component i. In summary, for a certain reaction, the reaction mass m r , specific reaction heat △ r H j , stoichiometric number v ij and the molar mass M of component i i The reaction exothermic power is q rx,j and reaction rate r j In direct proportion. In addition, according to the Van Hoff equation, the reaction rate doubles for every 10K increase in reaction temperature. First, adiabatic calorimetry is used to obtain the thermal stability data of the material at a certain temperature and time. It is clear that no exothermic decomposition behavior of the target material is detected under the set detection line. TMR is predicted based on the adiabatic tracking time and tracking temperature. ad and T Dx , expressed as formula (6):

[0061]

[0062] Where T Dx —The temperature corresponding to the time xh when the maximum reaction rate reaches xh under adiabatic conditions, in °C; T z—Adiabatic tracking undecomposed upper limit temperature, unit is ℃; t z —Adiabatic tracking undecomposed upper limit time, unit is min; obtain T Dx After the value range is set, the TMR at a certain temperature can be obtained. ad Numerical range, complete relevant reaction safety risk assessment and risk control.

[0063] and Figure 1 Corresponding to the method shown, the present invention also discloses a chemical reaction thermal risk assessment system for Figure 1 The implementation of the method, the specific structure is as follows Figure 2 As shown, the following steps are included:

[0064] Thermal decomposition characteristics acquisition module: used to obtain the thermal decomposition characteristics of the target material at different temperatures through adiabatic calorimetry;

[0065] Thermal decomposition behavior occurrence judgment module: used to determine, based on thermal decomposition characteristics, that no thermal decomposition behavior of the target material is detected at a set detection line;

[0066] Risk assessment and control module: used to predict T based on adiabatic tracking time and tracking temperature Dx , get T Dx After the value range is set, the TMR at a certain temperature can be obtained. ad Numerical range, complete relevant reaction safety risk assessment and risk control.

[0067] Finally, this embodiment discloses a computer storage medium, on which a computer program is stored. When the computer program is executed by a processor, any one of the steps of a chemical reaction thermal risk assessment method is implemented.

[0068] Example 2

[0069] Process conditions: add 400g of water to the reactor, reaction temperature T p The temperature is 25-35℃, 100g of acetic anhydride is added dropwise, the feeding time is 2h, and the temperature is kept for 1h after the feeding is completed. The maximum technical temperature MTT of the system is the bubble point of the system, and the maximum temperature MTSR that the process reaction can reach is 64.5℃. The adiabatic calorimetry test results show that within the test range of 300℃, there is no obvious exothermic signal of the system material at the end point of the acetic anhydride hydrolysis reaction, the adiabatic tracing undecomposed upper limit temperature is 290℃, and the adiabatic tracing undecomposed upper limit time is 30min. The test results are as follows Figure 3 As shown:

[0070] Use Formula 6 to obtain T D24 , the calculation process is as follows:

[0071]

[0072] Adiabatic accelerating calorimeter was used to carry out constant temperature experiments to verify the above experimental results. Figure 4 As shown:

[0073] The test results show that the acetic anhydride hydrolysis reaction endpoint system material did not decompose at 245°C for 24 hours, which is different from the acetic anhydride hydrolysis reaction endpoint system material T D24 The results are consistent at >244.2℃. This patented method is accurate and reliable.

[0074] The above data were used to evaluate the possibility of uncontrolled reaction and the hazard level of reaction process. The results are as follows:

[0075] Utilizing TMR ad The possibility of a runaway reaction in the acetic anhydride hydrolysis reaction was evaluated and the results are summarized in the table below.

[0076] Table 1 Results of evaluation of the possibility of uncontrolled reaction

[0077]

[0078] The MTSR of the acetic anhydride hydrolysis reaction is 64.5°C, and the corresponding maximum reaction rate reaches time greater than 24 hours. The possibility of uncontrolled reaction is "level 1", which is rare. Once cooling failure occurs, there is enough time for human disposal of uncontrolled reaction, resulting in a low probability of accident.

[0079] The temperature parameters of the acetic anhydride hydrolysis reaction process obtained from the reaction risk study are summarized in the table below.

[0080] Table 2 Summary of reaction process hazard assessment data

[0081]

[0082] The acetic anhydride hydrolysis reaction process was evaluated and the results are summarized in the table below.

[0083] Table 3 Results of reaction process hazard assessment

[0084]

[0085] According to the process hazard assessment results, it can be seen that the process hazard level of acetic anhydride hydrolysis reaction is "level 1", and the reaction hazard is relatively low. MTSR is less than MTT and T D24 When the system is heated to 100 °C, the system will not cause secondary decomposition of the material, nor will it cause the reaction material to boil violently and rush. However, it is still necessary to avoid the reaction material being heated for a long time to avoid reaching the MTT.

[0086] Example 3

[0087] Process conditions: At room temperature, add 5% by mass of tert-butyl peroxide material (95% water) to the reactor and conduct adiabatic calorimetry. The test results show that when the sample is heated to 118.5°C, there is an obvious exothermic signal and the sample undergoes exothermic decomposition. Within the test range of 118.5-130.4°C, the heat release is 60 J / g (based on the sample mass), the temperature rises by 11.9°C, the maximum temperature rise rate reaches 0.1°C / min at 121.6°C, and the maximum pressure rise rate reaches 121.3°C, and the maximum pressure rise rate is less than 0.01 MPa / min. Through kinetic research, under adiabatic conditions, the temperature T corresponding to the maximum reaction rate of 5% tert-butyl hydroperoxide when the time is 2h D2 113℃, T D4 108℃, T D8 102℃, T D24 94℃, T D168 It is 81°C (system Phi is 1.05).

[0088] Test results such as Figure 5 and Figure 6 As shown:

[0089] According to the adiabatic accelerated calorimetry test results, the upper limit temperature of adiabatic tracking without decomposition is 113°C, and the upper limit time of adiabatic tracking without decomposition is 30 minutes. Formula 6 is used to obtain T D4 , the calculation process is as follows:

[0090]

[0091] Adiabatic accelerating calorimeter was used to carry out constant temperature experiments to verify the above experimental results. Figure 7 As shown:

[0092] The test results show that 5% tert-butyl hydroperoxide does not decompose when kept adiabatically at 75°C for 4 hours. D4 >72.5℃, which is consistent with the T obtained by kinetic study method. D4 The data range is consistent, and this patented method is accurate and reliable.

[0093] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0094] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for quickly obtaining the important risk control parameter TMR, characterized in that: The following steps are involved: Obtain the thermal decomposition characteristics of the target material at different temperatures through adiabatic calorimetry testing; Determining based on the thermal decomposition characteristics that no thermal decomposition behavior of the target material is detected at the set detection line; Predict T based on adiabatic tracking time and tracking temperature Dx , get T Dx After the value range is set, the TMR at a certain temperature can be obtained. ad Numerical range, complete relevant reaction safety risk assessment and risk control.

2. A method for quickly obtaining the important risk control parameter TMR according to claim 1, characterized in that: Predict T based on adiabatic tracking time and tracking temperature Dx , the expression is as follows: Where, T Dx It represents the temperature corresponding to the maximum reaction rate reaching time x hours under adiabatic conditions; T z Indicates the upper limit temperature of adiabatic tracking without decomposition; t z Indicates the upper limit time for adiabatic tracking to not decompose.

3. A method for quickly obtaining the important risk control parameter TMR according to claim 1, characterized in that: The target material undergoes a reaction, and the reaction kinetics are as follows: Where r j represents the reaction rate, k j represents the reaction rate constant; C i represents the concentration of component i in the reaction system; m i represents the reaction order of component i.

4. A method for quickly obtaining the important risk control parameter TMR according to claim 3, characterized in that: Reaction rate constant k j Expressed as: Where k j,0 represents the pre-exponential factor; E a,j represents the reaction activation energy, R represents the molar gas constant; T r Indicates the reaction temperature.

5. A method for quickly obtaining the important risk control parameter TMR according to claim 3, characterized in that: The concentration of component i in the reaction system is expressed as: Where N i represents the number of moles of component i, m r Indicates the quality of the reaction system.

6. A method for quickly obtaining the important risk control parameter TMR according to claim 3, characterized in that: The generation rate R of component i in the reaction system i Expressed as: In the formula, R i represents the generation rate of component i in reaction j; v ij represents the stoichiometric number of component i in reaction j; m r Indicates the quality of the reaction system.

7. A method for quickly obtaining the important risk control parameter TMR according to claim 3, characterized in that: Relating reaction thermodynamics to reaction kinetics, the reaction power q rx,j Expressed as: Where q rx,j Represents reaction power; r H j Represents specific reaction heat; M i Indicates molar mass; m i represents the reaction order of component i.

8. A system for quickly acquiring the important risk control parameter TMR, characterized in that: The following steps are involved: Thermal decomposition characteristics acquisition module: used to obtain the thermal decomposition characteristics of the target material at different temperatures through adiabatic calorimetry; Thermal decomposition behavior occurrence judgment module: used to determine, based on thermal decomposition characteristics, that no thermal decomposition behavior of the target material is detected at a set detection line; Risk assessment and control module: used to predict T based on adiabatic tracking time and tracking temperature Dx , get T Dx After the value range is set, the TMR at a certain temperature can be obtained. ad Numerical range, complete relevant reaction safety risk assessment and risk control.

9. A computer storage medium, characterized in that: The computer storage medium stores a computer program, and when the computer program is executed by the processor, the steps of a method for quickly obtaining an important risk control parameter TMR as described in any one of claims 1 to 7 are implemented.

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