Risk control method and system for Grignard reagent production process

Abstract

The invention discloses a risk control method and system for a Grignard reagent production process, and relates to the technical field of chemical safety and engineering. Comprising the following steps: obtaining Grignard reagent synthesis reaction heat balance data and Grignard reagent synthesis system material potential decomposition risk information through reaction safety risk analysis; determining a dangerous scene of the Grignard reagent production process; and establishing a Grignard reagent risk control model based on the heat balance data, the material potential decomposition risk information and the dangerous scene, obtaining risk control parameters, and realizing risk control of the Grignard reagent production process. Thermodynamic quantitative data in the Grignard reagent synthesis reaction process is obtained through testing, a potential risk scene in the Grignard reagent production stage is further determined through scene analysis, risk control measures are established according to dangerous scene characteristics, and the safety problem of the Grignard reagent production process is solved.

Description

Technical Field

[0001] The invention relates to the fields of chemical safety technology and engineering technology, and in particular to a risk control method and system for a Grignard reagent production process. Background Art

[0002] The main raw materials for the preparation of Grignard reagents are halogenated hydrocarbons and magnesium metal. The halogenated hydrocarbons are usually chloroalkanes or bromoalkanes. During the reaction, the magnesium element in the system is gradually consumed, and finally a Grignard reagent is generated. Its general formula is RMgX, where R represents an alkyl group and X represents a halogen. Grignard reagents are widely used in industries such as medicine, pesticides, and material synthesis. They are extremely active in chemical properties and can react chemically with air, carbon dioxide, water, etc. The synthesis process of Grignard reagents is usually highly exothermic, and a large amount of heat is released during the reaction. If the reaction heat cannot be removed in time, thermal runaway of the reaction is very likely to occur, resulting in over-temperature and over-pressure of the system, causing safety accidents.

[0003] In the prior art, a hydrogen risk control system and control method for a small power nuclear reactor containment (CN104979020B) discloses a hydrogen risk control system and control method for a small power nuclear reactor containment, which injects inert gas into a small steel containment of a small power nuclear reactor and combines a passive hydrogen elimination device to ensure that the gas mixture in the containment is in a non-flammable state, thereby eliminating the risk of hydrogen combustion and explosion. However, the above-mentioned method is only applicable to hydrogen gas environments and is not suitable for risk control of Grignard reagent production processes. At present, no risk control method for Grignard reagent production processes has been found in the prior art.

[0004] Therefore, in view of the safety risks existing in the preparation stage of Grignard reagent, a risk control method and system for the production process of Grignard reagent is proposed to solve the difficulties existing in the prior art, which is an urgent problem to be solved by those skilled in the art. Summary of the invention

[0005] In view of this, the present invention provides a risk control method and system for the Grignard reagent production process, which obtains quantitative thermodynamic data of the Grignard reagent synthesis reaction process through testing, further determines the potential risk scenarios in the Grignard reagent production stage through scenario analysis, and establishes risk control measures according to the characteristics of the dangerous scenarios to solve the safety problems of the Grignard reagent production process.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A risk control method for a Grignard reagent production process comprises the following steps:

[0008] Obtain data: Obtain the heat balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system through reaction safety risk analysis;

[0009] Determine the scenario: Determine the hazardous scenario of the Grignard reagent production process;

[0010] Risk control: A risk control model for Grignard reagent is established based on thermal balance data, potential material decomposition risk information and hazardous scenarios to obtain risk control parameters and achieve risk control of the Grignard reagent production process.

[0011] Optionally, the specific contents of obtaining the heat balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system are:

[0012] According to the process information of the Grignard reagent preparation reaction, a reaction calorimeter is used to carry out the test to obtain the thermal balance data of the Grignard reagent preparation reaction process;

[0013] An adiabatic accelerating calorimeter is used to conduct thermal stability tests on the materials of the Grignard reagent synthesis system at the reaction endpoint to obtain the thermal decomposition characteristics of the materials in the reaction system, to clarify whether thermal runaway of the Grignard reagent preparation reaction will cause secondary decomposition of the materials, and to obtain information on the potential decomposition risk of the materials.

[0014] Optionally, the obtained heat balance data of the Grignard reagent synthesis reaction includes heat release rate and heat accumulation data.

[0015] Optionally, the specific contents of the hazardous scenarios of the Grignard reagent production process are determined as follows:

[0016] Based on the thermal balance data and the potential decomposition risk information of the materials, the key safety points and cut-off control points are determined, and the causes of the overpressure risk caused by thermal runaway of the Grignard reagent preparation reaction are analyzed. It is determined that the dangerous scenario of the Grignard reagent preparation reaction is the end of feeding and the largest amount of material in the reaction system.

[0017] Optionally, a Grignard reagent risk control model is established based on heat balance data, potential material decomposition risk information and hazardous scenarios to obtain risk control parameters. The specific contents of risk control for the Grignard reagent production process are as follows:

[0018] Calculate the Grignard reagent risk control model through the release rate, release mass flow rate and release area;

[0019] The discharge rate F is calculated as follows:

[0020]

[0021] The discharge mass flow rate G is calculated as follows:

[0022]

[0023] The discharge area A is calculated as follows:

[0024]

[0025] Where V is the reactor volume in m 3 , m0 is the mass of the reactant, in kg, T s is the temperature inside the reactor when the discharge port is opened, in °C, is the slope of the pressure-temperature curve of the mixed material in the reactor, C pf is the specific heat capacity of liquid, in kJ / kg·K, ΔT is the adiabatic temperature rise from the discharge pressure to the design pressure, in K, and q is the average heat release rate per unit mass, in W / kg.

[0026] A risk control system for a Grignard reagent production process, applying any of the above-mentioned risk control methods for a Grignard reagent production process, comprising: a data acquisition module, a scenario determination module and a risk control module;

[0027] A data acquisition module is connected to the input end of the scenario determination module and is used to obtain the thermal balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system through reaction safety risk analysis;

[0028] A scenario determination module, connected to the input end of the risk control module, is used to determine the hazardous scenario of the Grignard reagent production process;

[0029] The risk control module is used to establish a Grignard reagent risk control model based on thermal balance data, material potential decomposition risk information and hazardous scenarios, obtain risk control parameters, and achieve risk control of the Grignard reagent production process.

[0030] It can be seen from the above technical solution that, compared with the prior art, the present invention provides a risk control method and system for Grignard reagent production process, which has the following beneficial effects:

[0031] (1) The present invention can solve the safety problem caused by thermal runaway of the Grignard reagent production, thereby ensuring production safety;

[0032] (2) The present invention obtains quantitative thermodynamic data of the Grignard reagent synthesis reaction process through testing, further determines potential risk scenarios in the Grignard reagent production stage through scenario analysis, establishes risk control measures based on the characteristics of dangerous scenarios, and solves the safety issues of the Grignard reagent production process. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] 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.

[0034] Figure 1 A flow chart of a risk control method for a Grignard reagent production process provided by the present invention;

[0035] Figure 2 A time-temperature-pressure curve diagram of adiabatic calorimetry test of materials in a system for preparing a reaction end point of a Grignard reagent provided by the present invention;

[0036] Figure 3 A partial enlarged view of the time-temperature-pressure curve of the adiabatic calorimetric test of the material of the Grignard reagent preparation reaction endpoint system provided by the present invention;

[0037] Figure 4 This is a calorimetric test diagram of the Grignard reagent preparation reaction provided by the present invention. DETAILED DESCRIPTION

[0038] 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.

[0039] Reference Figure 1 As shown, the present invention discloses a risk control method for a Grignard reagent production process, comprising the following steps:

[0040] Obtain data: Obtain the heat balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system through reaction safety risk analysis;

[0041] Determine the scenario: Determine the hazardous scenario of the Grignard reagent production process;

[0042] Risk control: A risk control model for Grignard reagent is established based on thermal balance data, potential material decomposition risk information and hazardous scenarios to obtain risk control parameters and achieve risk control of the Grignard reagent production process.

[0043] Furthermore, the specific contents of obtaining the heat balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system are as follows:

[0044] According to the process information of the Grignard reagent preparation reaction, a reaction calorimeter is used to carry out the test to obtain the thermal balance data of the Grignard reagent preparation reaction process;

[0045] An adiabatic accelerating calorimeter is used to conduct thermal stability tests on the materials of the Grignard reagent synthesis system at the reaction endpoint to obtain the thermal decomposition characteristics of the materials in the reaction system, to clarify whether thermal runaway of the Grignard reagent preparation reaction will cause secondary decomposition of the materials, and to obtain information on the potential decomposition risk of the materials.

[0046] Furthermore, the heat balance data obtained for the Grignard reagent synthesis reaction include heat release rate and heat accumulation data.

[0047] Furthermore, the specific contents of the hazardous scenarios of the Grignard reagent production process are determined as follows:

[0048] Based on the thermal balance data and the potential decomposition risk information of the materials, the key safety points and cut-off control points are determined, and the causes of the overpressure risk caused by thermal runaway of the Grignard reagent preparation reaction are analyzed. It is determined that the dangerous scenario of the Grignard reagent preparation reaction is the end of feeding and the largest amount of material in the reaction system.

[0049] Furthermore, a risk control model for Grignard reagents is established based on thermal balance data, potential material decomposition risk information and hazardous scenarios, and risk control parameters are obtained. The specific contents of risk control for the Grignard reagent production process are as follows:

[0050] Calculate the Grignard reagent risk control model through the release rate, release mass flow rate and release area;

[0051] The discharge rate F is calculated as follows:

[0052]

[0053] The discharge mass flow rate G is calculated as follows:

[0054]

[0055] The discharge area A is calculated as follows:

[0056]

[0057] Where V is the reactor volume in m 3 , m0 is the mass of the reactant, in kg, T s is the temperature inside the reactor when the discharge port is opened, in °C, is the slope of the pressure-temperature curve of the mixed material in the reactor, C pf is the specific heat capacity of liquid, in kJ / kg·K, ΔT is the adiabatic temperature rise from the discharge pressure to the design pressure, in K, and q is the average heat release rate per unit mass, in W / kg.

[0058] In a specific embodiment, the following contents are included: through reaction safety risk analysis, the heat balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system are obtained; the dangerous scenarios of the Grignard reagent production process are determined; based on the heat balance data, the potential decomposition risk information of the materials and the dangerous scenarios, a Grignard reagent risk control model is established to obtain risk control parameters, so as to realize the risk control of the Grignard reagent production process.

[0059] The process conditions for the preparation reaction of the Grignard reagent are as follows: the reactor is loaded with 191.1 kg of magnesium chips and 573.3 kg of furan solvent, the reaction temperature is controlled at 50-55°C, a mixture of halogenated hydrocarbons and furan solvents is added dropwise, including 868.9 kg of halogenated hydrocarbons and 1414.2 kg of furan solvents, the addition time is about 2 hours, and the temperature is kept for 1-3 hours after the addition is completed.

[0060] Adiabatic calorimetry test was performed on the materials of the Grignard reagent preparation reaction endpoint system. The time-temperature-pressure curve and partial enlarged diagram of the adiabatic calorimetry test of the materials of the Grignard reagent preparation reaction endpoint system are shown in the figure. Figure 2 and Figure 3 As shown, the adiabatic accelerated calorimetry test results show that within the test range of 400°C, the Grignard reagent preparation reaction endpoint system material undergoes two stages of exothermic decomposition behavior. The starting exothermic decomposition temperature of the first stage of the exothermic decomposition process is 202.6°C, the adiabatic temperature rise is 1.1K, and the decomposition heat is 10J / g; the starting exothermic decomposition temperature of the second stage of the exothermic decomposition process is 278.4°C, the adiabatic temperature rise is 107.2K, and the decomposition heat is 380J / g. The research results show that the exothermic decomposition behavior of the Grignard reagent preparation reaction occurs after 200°C, which is far away from the process temperature range of 50-55°C. Therefore, when performing subsequent risk control parameter calculations, it is not necessary to consider the secondary decomposition behavior of the Grignard reagent preparation reaction endpoint system material. Further reaction calorimetry tests were carried out on the Grignard reagent preparation reaction to obtain the exothermic rate and heat accumulation data of the Grignard reaction process. The reaction calorimetry test results are shown as follows. Figure 4 As shown, Figure 4The horizontal axis is time, the unit is minutes, the left vertical axis is the reaction temperature and exothermic power, the unit of reaction temperature is ℃, the unit of exothermic power is w, the right vertical axis is the feed mass and apparent reaction heat, the unit of feed mass is g, and the unit of apparent reaction heat is kJ. The reaction calorimetry test results show that after the halogenated hydrocarbon and furan solvent mixture is added to the reaction system, the system immediately releases heat, the reaction exothermic power increases rapidly and then decreases rapidly to a stable state, the reaction exothermic power is relatively stable during the entire feeding process, and after the feeding is completed, the reaction exothermic power decreases rapidly to 0w. The reaction calorimetry study results show that the preparation reaction of the Grignard reagent is feed-controlled, the raw material conversion is very fast, and the release of reaction heat is completely determined by the feeding rate of the halogenated hydrocarbon and furan solvent mixture. When the feeding is stopped, the reaction exothermic power drops to 0. This means that there is almost no heat accumulation in the reaction.

[0061] According to the reaction calorimetry and thermal stability test data, the causes of overpressure risk caused by thermal runaway of the Grignard reagent preparation reaction are analyzed. There is almost no heat accumulation in the Grignard reagent preparation reaction. As long as normal control is maintained, thermal runaway of the reaction will not occur. The instability of the product in this system has little to do with the safety of the system. The amount and addition rate of halogenated hydrocarbons are crucial to the progress of this reaction process and need to be strictly monitored and controlled. The dangerous scenarios that may lead to sudden risks in the Grignard reagent preparation reaction process are as follows:

[0062] a) Cooling failure at normal feeding rate; b) Stirring failure at normal feeding rate.

[0063] In any of the above cases, the heat released by the reaction will lead to an increase in pressure and temperature, which will eventually cause the reactor vent to open and release pressure.

[0064] The cooling failure and stirring failure scenarios were selected to conduct risk control measures research. The reactor equipment parameters are as follows: The volume is 7.54m 3 , design temperature 80℃, design pressure 0.43MPa, discharge port starting pressure 0.36MPa, and the released steam / liquid is discharged through a pipe from the reactor to the discharge tank.

[0065] The discharge rate F is calculated as follows:

[0066]

[0067] The discharge mass flow rate G is calculated as follows:

[0068]

[0069] The discharge area A is calculated as follows:

[0070]

[0071] Where V is the reactor volume in m 3 , m0 is the mass of the reactant, in kg, T s is the temperature inside the reactor when the discharge port is opened, in °C, is the slope of the pressure-temperature curve of the mixed material in the reactor, C pf is the specific heat capacity of liquid, in kJ / kg·K, ΔT is the adiabatic temperature rise from the discharge pressure to the design pressure, in K, and q is the average heat release rate per unit mass, in W / kg.

[0072] In summary, cooling failure or stirring failure is a risk situation for the Grignard reagent preparation reaction. In order to avoid accidents caused by sudden risks in the reaction process, a discharge port needs to be set on the Grignard reagent preparation reactor. When cooling failure or stirring failure occurs, the feed is cut off immediately. When the system pressure reaches 0.36MPa, the discharge port is opened. The required discharge area is 2.268×10-3m 2 Under this condition, the material can be discharged through the discharge port to effectively avoid the risk of reactor overpressure and ensure the safety of the Grignard reagent preparation reactor.

[0073] and Figure 1 Corresponding to the method, an embodiment of the present invention further provides a risk control system for a Grignard reagent production process, specifically comprising: a data acquisition module, a scenario determination module and a risk control module;

[0074] A data acquisition module is connected to the input end of the scenario determination module and is used to obtain the thermal balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system through reaction safety risk analysis;

[0075] A scenario determination module, connected to the input end of the risk control module, is used to determine the hazardous scenario of the Grignard reagent production process;

[0076] The risk control module is used to establish a Grignard reagent risk control model based on thermal balance data, material potential decomposition risk information and hazardous scenarios, obtain risk control parameters, and achieve risk control of the Grignard reagent production process.

[0077] 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.

[0078] 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 risk control method for a Grignard reagent production process, characterized in that: The following steps are involved: Obtain data: Obtain the heat balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system through reaction safety risk analysis; Determine the scenario: Determine the hazardous scenario of the Grignard reagent production process; Risk control: A risk control model for Grignard reagent is established based on thermal balance data, potential material decomposition risk information and hazardous scenarios to obtain risk control parameters and achieve risk control of the Grignard reagent production process.

2. The risk control method for a Grignard reagent production process according to claim 1, characterized in that: The specific contents of obtaining the heat balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system are as follows: According to the process information of the Grignard reagent preparation reaction, a reaction calorimeter is used to carry out the test to obtain the thermal balance data of the Grignard reagent preparation reaction process; An adiabatic accelerating calorimeter is used to conduct thermal stability tests on the materials of the Grignard reagent synthesis system at the reaction endpoint to obtain the thermal decomposition characteristics of the materials in the reaction system, to clarify whether thermal runaway of the Grignard reagent preparation reaction will cause secondary decomposition of the materials, and to obtain information on the potential decomposition risk of the materials.

3. The risk control method for a Grignard reagent production process according to claim 1, characterized in that: The heat balance data obtained for the Grignard reagent synthesis reaction include heat release rate and heat accumulation data.

4. The risk control method for a Grignard reagent production process according to claim 1, characterized in that: The specific contents of determining the hazardous scenarios of the Grignard reagent production process are: Based on the thermal balance data and the potential decomposition risk information of the materials, the key safety points and cut-off control points are determined, and the causes of the overpressure risk caused by thermal runaway of the Grignard reagent preparation reaction are analyzed. It is determined that the dangerous scenario of the Grignard reagent preparation reaction is the end of feeding and the largest amount of material in the reaction system.

5. The risk control method for a Grignard reagent production process according to claim 1, characterized in that: Based on the heat balance data, the potential decomposition risk information of materials and the dangerous scenarios, the risk control model of Grignard reagent is established to obtain the risk control parameters. The specific contents of risk control of Grignard reagent production process are as follows: Calculate the Grignard reagent risk control model through the release rate, release mass flow rate and release area; The discharge rate F is calculated as follows: The discharge mass flow rate G is calculated as follows: The discharge area A is calculated as follows: Where V is the reactor volume in m 3 , m0 is the mass of the reactant, in kg, T s is the temperature in the reactor when the discharge port is opened, in °C, is the slope of the pressure-temperature curve of the mixed material in the reactor, C pf is the liquid specific heat capacity, unit is kJ / kg·K, ΔT is the adiabatic temperature rise from the discharge pressure to the design pressure, unit is K, q is the average heat release rate per unit mass, unit is W / kg.

6. A risk control system for a Grignard reagent production process, characterized in that: A risk control method for a Grignard reagent production process according to any one of claims 1 to 5, comprising: a data acquisition module, a scenario determination module and a risk control module; A data acquisition module is connected to the input end of the scenario determination module and is used to obtain the thermal balance data of the Grignard reagent synthesis reaction and the potential decomposition risk information of the materials in the Grignard reagent synthesis system through reaction safety risk analysis; A scenario determination module, connected to the input end of the risk control module, is used to determine the hazardous scenario of the Grignard reagent production process; The risk control module is used to establish a Grignard reagent risk control model based on thermal balance data, material potential decomposition risk information and hazardous scenarios, obtain risk control parameters, and achieve risk control of the Grignard reagent production process.

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