Chemical compatibility testing and grading method

Abstract

The invention belongs to the technical field of chemical use and storage management risk assessment, and particularly discloses a chemical compatibility test grading method. The method comprises the following steps: S1, mixing and testing chemicals, and if heat production, gas production or chemical quality change phenomena before and after testing exist after mixing of the two chemicals, determining that the two chemicals belong to A-level incompatibility; s2, constant-temperature heat production testing is conducted, and if the unit heat production amount of the mixture is larger than or equal to 1 J / g compared with the unit heat production amount of any one of the two chemicals, it is judged that the mixture belongs to B-level incompatibility. S3, carrying out heat and gas production screening test, and if a gas production phenomenon exists, carrying out vacuum stability test; and if the heat release phenomenon exists, carrying out a constant-rate temperature rise test. And S4, performing a vacuum stability test, and if the gas production volume of the mixture is increased compared with the gas production volume of any one of the two chemicals, judging that the two chemicals belong to C-grade incompatibility. And S5, carrying out constant-rate heating test. The method is suitable for compatibility evaluation of mixtures with unknown or complex components.

Description

Technical Field

[0001] The invention belongs to the technical field of risk assessment of chemical use and storage management, and in particular relates to a chemical compatibility test grading method. Background Art

[0002] Chemicals may be mixed due to human factors, environmental factors or other factors during production, use, transportation and storage. It is safe to mix compatible chemicals. Accidental mixing of incompatible chemicals may release heat, produce toxic gases, explode, etc., resulting in serious accidental consequences. In order to avoid such accidents from happening again, it is necessary to clarify the compatibility level of chemicals.

[0003] Most of the existing chemical compatibility assessment methods are based on the composition of the chemicals and their categories (such as acid, base, etc.). For example, the US Coast Guard Incompatibility Chart proposed by the US Coast Guard in 1983 divides chemicals into 2 groups and 43 categories. Later, the Office of Response and Recovery of the National Oceanic and Atmospheric Administration (NOAA) of the United States, the Environmental Protection Agency, the Chemical Process Safety Center, etc. developed the Chemical Reactivity Worksheet (CRW), which divides chemicals into 68 reactive groups for compatibility queries. The above method is only applicable to chemicals with clear composition properties, and is not applicable to chemicals with unknown composition or complex mixtures.

[0004] In addition, the specific characteristics of chemical incompatibility are of great significance to chemical management. For example, two chemicals that may explode when mixed need to be strictly isolated and stored, while two chemicals that may produce slight heat when mixed do not require such strict management. Therefore, the compatibility classification of chemicals is very important.

[0005] Based on the above problems, the present invention designs a chemical compatibility test and grading method, which can determine the compatibility of the two chemicals and divide the compatibility grades by testing the heat and gas generation after mixing the chemicals and the difference in properties between the mixture and the original chemicals through logical judgment. The test method can be completed using only a small amount of chemicals. Summary of the invention

[0006] The purpose of the present invention is to provide a chemical compatibility test and grading method, which effectively solves the problem that most existing chemical compatibility assessment methods are based on chemical composition and classification (such as acid, alkali, etc.) and are not suitable for mixtures with unknown or complex components.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is:

[0008] A chemical compatibility test grading method comprises the following steps:

[0009] S1. Conduct chemical mixing test.

[0010] Take appropriate amounts of two chemicals and place them in a constant temperature closed reaction box. At this time, the two chemicals do not touch each other. After the system temperature stabilizes at the set value, mix the two chemicals.

[0011] The test temperature is about 10℃ higher than the actual working environment temperature. If there is no reference temperature, the constant temperature setting temperature is between 40℃ and 100℃, or set according to test needs.

[0012] By monitoring the heat flow and system pressure or the change in chemical mass before and after the test, the heat generation, gas production and reaction conditions of the system after the mixing begins are evaluated. If there is a certain amount of heat generation, gas production or a change in chemical mass before and after the test after the two chemicals are mixed, the two chemicals are determined to be Class A incompatible, and the compatibility is graded according to the heat generation, gas production or the degree of change in chemical mass before and after the test. When the evaluation is completed, if the two chemicals do not generate heat or gas after mixing, the change in chemical mass before and after the test is not considered at this time, and the test continues according to step S2.

[0013] S2. Conduct constant temperature heat generation tests on chemicals and their mixtures.

[0014] A calorimetric device is used to perform a constant temperature heat generation test on a certain amount of two chemicals and their mixture. The test temperature is about 10°C to 50°C higher than the test temperature in step S1. The test time is 4 to 48 hours, which can also be set according to test needs.

[0015] The test mass of the two chemicals and the test mass of the mixture of the two chemicals as well as the temperature and other experimental conditions were kept consistent, and three heat flow-time curves were measured at a constant temperature.

[0016] If the unit heat generation of the mixture is greater than that of either of the two chemicals and the increase is ≥1J / g, the two chemicals are judged to be Class B incompatible, and the compatibility is graded according to the measured unit heat generation; if the peak heat generation power of the heat flux of the mixture is greater than that of either of the two chemicals and the increase is ≥10mW, the two chemicals are judged to be Class B incompatible, and the compatibility is graded according to the measured peak heat generation power of the heat flux; otherwise, subsequent testing should be carried out.

[0017] S3. Conduct a heat and gas generation screening test on a mixture of two chemicals.

[0018] A rapid screening calorimeter or an adiabatic accelerating calorimeter is used to perform a heat and gas generation screening test on a mixture of two chemicals. The test starting temperature is the test temperature of the constant temperature heat generation test described in step S2, the test maximum temperature is 400°C to 600°C, and the test mass of the mixture of the two chemicals is 0.1mg to 50g. The test obtains the starting exothermic temperature, heat flow-time curve or heat flow-temperature curve and pressure-time curve or pressure-temperature curve of the mixture.

[0019] If the pressure-time curve or the pressure-temperature curve of the mixture fluctuates, gas generation occurs, and a vacuum stability test is performed according to step S4.

[0020] If there is no gas generation, but the heat flow-time curve or the heat flow-temperature curve of the mixture fluctuates, heat release occurs, and a constant rate heating test is performed according to step S5.

[0021] If there is no gas generation and no heat release, the two chemicals are considered compatible.

[0022] S4. Conduct vacuum stability tests on chemicals and their mixtures.

[0023] A vacuum stability tester is used to test a certain amount of two chemicals and their mixtures respectively. The test temperature is based on the heat and gas production screening test of the mixture of the two chemicals described in step S3. A temperature that is 10°C higher than the temperature corresponding to the initial point of the pressure fluctuation in the pressure-time curve or the pressure-temperature curve of the mixture obtained in step S3 is selected. The experimental conditions such as the test quality and temperature of each chemical and its mixture are kept consistent. A pressure sensor is used to monitor the gas production in the chamber. The test can be terminated when the pressure fluctuation stabilization time exceeds 15 minutes. The gas production is converted from a pressure signal to an electrical signal, and the gas production volume is automatically calculated through the monitored temperature and pressure parameters.

[0024] Compare the gas production volumes of the two chemicals and their mixture or the pressure rise during the test process. If the gas production volume of the mixture is larger than the gas production volume of any one of the two chemicals, the two chemicals are determined to be Class C incompatible, and the compatibility is graded according to the increment of the unit gas production volume of the mixture compared to the unit gas production volume of the chemical with a lower unit gas production volume of the two chemicals; if the pressure rise during the test process of the mixture is larger than the unit pressure rise of any one of the two chemicals, the two chemicals are determined to be Class C incompatible, and the compatibility is graded according to the increment of the unit pressure rise of the mixture compared to the unit pressure rise of the chemical with a lower unit pressure rise of the two chemicals; otherwise, perform a constant rate heating test in accordance with step S5.

[0025] S5. Conduct constant rate temperature rise tests on chemicals and their mixtures.

[0026] A calorimetric device is used to test a certain amount of two chemicals and their mixture. If the substance to be tested is a volatile substance, it cannot be tested with an open device. The test starting temperature is the test temperature of the constant temperature heat generation test described in step S2. The maximum test temperature is 400°C to 600°C, or is set according to test needs.

[0027] The experimental conditions such as the test mass and temperature of the two chemicals and their mixture are kept consistent, and the test obtains the initial exothermic temperature, exothermic heat, exothermic peak and heat flow-time curve or heat flow-temperature curve of the two chemicals and their mixture under the test conditions.

[0028] Compare the initial exothermic temperature, exothermic heat, exothermic peak and heat flow-time curve or heat flow-temperature curve of the two chemicals and their mixture. If the initial exothermic temperature of the mixture under the test conditions is lower than the initial exothermic temperature of the two chemicals under the test conditions, the two chemicals are judged to be Class D incompatible, and the compatibility is graded according to the reduction in the measured initial exothermic temperature of the mixture under the test conditions compared with the one of the two chemicals with the lower initial exothermic temperature under the test conditions.

[0029] If the heat release of the mixture under the test conditions is higher than the heat release of both chemicals under the test conditions, the two chemicals are judged to be Class D incompatible, and the compatibility is graded based on the increase in the measured heat release of the mixture under the test conditions compared to the lower heat release of the two chemicals under the test conditions.

[0030] If the temperature corresponding to the heat flow peak of the mixture under the test conditions is lower than the temperatures corresponding to the heat flow peaks of the two chemicals under the test conditions, the two chemicals are judged to be D-level incompatible, and the compatibility is graded according to the amount of reduction in the temperature corresponding to the heat flow peak of the mixture under the test conditions compared to the temperature corresponding to the lower heat flow peak of the two chemicals under the test conditions.

[0031] If the heat flux peak heat generation power of the mixture under the test conditions is higher than the heat flux peak heat generation power of any one of the two chemicals under the test conditions, the two chemicals are judged to be D-level incompatible, and the compatibility is graded according to the increase in the heat flux peak heat generation power of the mixture under the test conditions compared to the chemical with the lower heat flux peak heat generation power under the test conditions; otherwise, the two chemicals are judged to be compatible.

[0032] Furthermore, in step S1, the test mass of the chemical is 0.1 mg to 50 g, and the system temperature setting value is -30°C to 90°C.

[0033] Furthermore, the calorimetric equipment in step S2 and step S5 is any one of a differential scanning calorimeter DSC, a microcalorimeter C80 and an adiabatic calorimeter ARC.

[0034] Furthermore, the test mass in step S2 is 0.1 mg to 50 g.

[0035] Furthermore, in step S4, the test mass is 0.1 mg to 50 g, and the test temperature is between 40° C. and 200° C.

[0036] Furthermore, in step S5, the test mass is 0.1 mg to 50 g, and the test heating rate is 0.1 to 10° C. / s.

[0037] Furthermore, the Class A incompatibility is subdivided according to the heat generation or gas generation or the degree of change in the quality of the chemical before and after the test as follows:

[0038] Heat generation power (mW) Compatibility classification ＞500 A1 level incompatible 100～500 A2 level incompatible 50～100 A3 level incompatible 10～50 A4 level incompatible ＜10 Compatible

[0039] Heat production (J / g) Compatibility classification ≥3000 A1 level incompatible 1200～3000 A2 level incompatible 400～1200 A3 level incompatible ＜400 A4 level incompatible 0 Compatible

[0040]

[0041]

[0042] Pressure rise increment (MPa / g) Compatibility classification ＞2 A1 level incompatible 2～5 A2 level incompatible 0.5～2 A3 level incompatible 0.1～0.5 A4 level incompatible ＜0.1 Compatible

[0043] Quality loss Compatibility classification ＞10％ A1 level incompatible 5％～10％ A2 level incompatible 1％～5％ A3 level incompatible 0.1％～1％ A4 level incompatible ＜0.1％ Compatible

[0044] Furthermore, the Class B incompatibility is subdivided according to the heat generation increment or the heat flux peak heat generation power increase value as follows:

[0045] Heat generation increment (J / g) Compatibility classification ≥300 B1 level incompatibility 100～200 B2 level incompatibility 20～100 B3 level incompatibility 1～20 B4 level incompatibility ＜1 Compatible

[0046] Peak heat flux and heat generation power increase value (mW) Compatibility classification ＞500 B1 level incompatibility 100～500 B2 level incompatibility 50～100 B3 level incompatibility 10～50 B4 level incompatibility ＜10 Compatible

[0047] Furthermore, the Class C incompatibility is subdivided according to the gas production volume increment or pressure rise increment as follows:

[0048] Gas production volume increment (mL / g) Compatibility classification ＞20 C1 level incompatible 10～20 C2 level incompatibility 5～10 C3 level incompatibility 1～5 C4 level incompatibility ＜1 Compatible

[0049] Pressure rise increment (MPa / g) Compatibility classification ＞2 C1 level incompatible 2～5 C2 level incompatibility 0.5～2 C3 level incompatibility 0.1～0.5 C4 level incompatibility ＜0.1 Compatible

[0050] Furthermore, the D-level incompatibility is subdivided according to the starting exothermic temperature reduction value or the heat release increase value or the temperature reduction value corresponding to the heat flux peak value or the heat flux peak heat generation power increase value as follows:

[0051]

[0052]

[0053] Heat release rise value (J / g) Compatibility classification ≥300 D1 level incompatibility 100～200 D2 level incompatibility 20～100 D3-level incompatibility 1～20 D4-level incompatibility ＜1 Compatible

[0054] Temperature drop corresponding to heat flow peak value (℃) Compatibility classification ＞10 D1 level incompatibility 10～50 D2 level incompatibility 5～10 D3-level incompatibility 2～5 D4-level incompatibility ＜2 Compatible

[0055]

[0056]

[0057] The beneficial technical effects of the present invention are:

[0058] (1) The present invention tests the heat and gas generation after chemical mixing and the difference in properties between the mixture and the original chemicals, and through logical judgment, clarifies the compatibility of the two and divides the compatibility levels. This solves the problem that most existing chemical compatibility assessment methods are based on chemical composition and classification (such as acid, alkali, etc.) and are not suitable for mixtures with unknown or complex components. This is of great significance to chemical management.

[0059] (2) The chemical compatibility test grading method provided by the present invention can be completed using only a small amount of chemicals, which is conducive to cost saving.

[0060] (3) The present invention has broad application prospects and can be applied to the fields of compatibility research of complex-component chemicals, scientific and safe management of chemicals, risk assessment of chemical mixing, or hierarchical management of incompatible chemical groups based on compatibility classification. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] In order to clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0062] Figure 1 It is a flowchart of the present invention;

[0063] Figure 2 is an exothermic curve diagram of a mixture of a 10% hydrochloric acid solution and a 1 mol / L sodium hydroxide solution in Example 1 of the present invention;

[0064] Figure 3 1 is a heat flow-time curve diagram of tar, light oil and a mixture of the two at a constant temperature in Example 2 of the present invention, wherein (a) is a heat flow-time curve diagram of tar, (b) is a heat flow-time curve diagram of light oil, and (c) is a heat flow-time curve diagram of a mixture of tar and light oil;

[0065] Figure 4is a curve chart of the heat and gas generation screening test results of the tar and light oil mixture in Example 2 of the present invention;

[0066] Figure 5 1 is a heat flow-temperature curve diagram of tar, light oil and a mixture of the two under test conditions in Example 2 of the present invention, wherein a is a heat flow-temperature curve diagram of tar, b is a heat flow-temperature curve diagram of light oil, and c is a heat flow-temperature curve diagram of a mixture of tar and light oil;

[0067] Figure 6 3 are heat flow-time curves of styrene tar, iron oxide and a mixture of the two at a constant temperature in Example 3 of the present invention, wherein (a) is a heat flow-time curve of styrene tar, (b) is a heat flow-time curve of iron oxide, and (c) is a heat flow-time curve of a mixture of styrene tar and iron oxide. DETAILED DESCRIPTION

[0068] The applicant of the present invention has designed a chemical compatibility test and grading method, which tests the heat and gas generation after chemical mixing and the difference in properties between the mixture and the original chemicals, and clarifies the compatibility of the two through logical judgment, and divides the compatibility grades. This test method can be completed using only a small amount of chemicals.

[0069] like Figure 1 As shown, a chemical compatibility test grading method comprises the following steps:

[0070] S1. Conduct chemical mixing test.

[0071] Take 0.1mg to 50g of each of the two chemicals and place them in a constant temperature closed reaction box. At this time, the two chemicals do not touch each other. After the system temperature stabilizes at the set value (the system temperature setting value is -30℃ to 90℃), mix the two chemicals.

[0072] The test temperature should be about 10°C higher than the actual working environment temperature. If there is no reference temperature, the constant temperature setting temperature is preferably between 40°C and 100°C, and can also be set according to test needs.

[0073] By monitoring the heat flow and system pressure or the change in chemical mass before and after the test, the heat generation, gas production and reaction conditions of the system after the mixing begins are evaluated. If there is a certain amount of heat generation, gas production or a change in chemical mass before and after the test after the two chemicals are mixed, the two chemicals are determined to be Class A incompatible, and the compatibility is graded according to the heat generation, gas production or the degree of change in chemical mass before and after the test. When the evaluation is completed, if the two chemicals do not generate heat or gas after mixing, the change in chemical mass before and after the test is not considered at this time, and the test continues according to step S2.

[0074] The A-level incompatibility is subdivided according to the heat generation or gas generation or the degree of change in the quality of the chemical before and after the test as shown in Tables 1 to 5 below:

[0075] Table 1 List of Class A incompatibility classifications based on heat generation power

[0076] Heat generation power (mW) Compatibility classification ＞500 A1 level incompatible 100～500 A2 level incompatible 50～100 A3 level incompatible 10～50 A4 level incompatible ＜10 Compatible

[0077] Table 2 A-level incompatibility classification list based on heat generation

[0078]

[0079]

[0080] Table 3 Class A incompatibility classification based on gas production volume

[0081] Gas production volume (mL / g) Compatibility classification ＞20 A1 level incompatible 10～20 A2 level incompatible 5～10 A3 level incompatible 1～5 A4 level incompatible ＜1 Compatible

[0082] Table 4 A-level incompatibility classification list based on pressure rise increment

[0083] Pressure rise increment (MPa / g) Compatibility classification ＞2 A1 level incompatible 2～5 A2 level incompatible 0.5～2 A3 level incompatible 0.1～0.5 A4 level incompatible ＜0.1 Compatible

[0084] Table 5 A-level incompatibility classification list based on mass loss

[0085] Quality loss Compatibility classification ＞10％ A1 level incompatible 5％～10％ A2 level incompatible 1％～5％ A3 level incompatible 0.1％～1％ A4 level incompatible ＜0.1％ Compatible

[0086] S2. Conduct constant temperature heat generation tests on chemicals and their mixtures.

[0087] A differential scanning calorimeter DSC or a microcalorimeter C80 or an adiabatic calorimeter ARC or other equipment that meets the test requirements is used to perform a constant temperature heat generation test on a certain amount of two chemicals and their mixture. The test temperature is preferably about 10°C to 50°C higher than the test temperature in step S1. The test time is 4 to 48 hours, which can also be set according to the test needs.

[0088] The test mass of the chemical and its mixture is preferably 0.1 mg to 50 g. The test mass of the two chemicals and the test mass of the mixture of the two chemicals and the temperature and other experimental conditions are kept consistent, and three heat flow-time curves are measured at a constant temperature.

[0089] If the unit heat generation of the mixture is greater than that of either of the two chemicals and the increase is ≥1J / g, the two chemicals are judged to be Class B incompatible, and the compatibility is graded according to the measured unit heat generation; if the peak heat generation power of the heat flux of the mixture is greater than that of either of the two chemicals and the increase is ≥10mW, the two chemicals are judged to be Class B incompatible, and the compatibility is graded according to the measured peak heat generation power of the heat flux; otherwise, subsequent testing should be carried out.

[0090] The Class B incompatibility is subdivided according to the heat generation increment or the heat flux peak heat generation power increase value as shown in Table 6 and Table 7 below:

[0091] Table 6 Class B incompatibility classification based on heat generation increment

[0092] Heat generation increment (J / g) Compatibility classification ≥300 B1 level incompatibility 100～200 B2 level incompatibility 20～100 B3 level incompatibility 1～20 B4 level incompatibility ＜1 Compatible

[0093] Table 7 Class B incompatibility classification list based on the peak heat flux heat generation power increase value

[0094] Peak heat flux and heat generation power increase value (mW) Compatibility classification ＞500 B1 level incompatibility 100～500 B2 level incompatibility 50～100 B3 level incompatibility 10～50 B4 level incompatibility ＜10 Compatible

[0095] S3. Conduct a heat and gas generation screening test on a mixture of two chemicals.

[0096] A rapid screening calorimeter or an adiabatic accelerating calorimeter or other equipment that meets the test requirements is used to perform a heat and gas generation screening test on the mixture of the two chemicals. The test starting temperature is preferably the test temperature in the constant temperature heat generation test in step S2, and the test maximum temperature is 400°C to 600°C. The test mass of the mixture of the two chemicals is preferably 0.1mg to 50g. The test obtains the starting exothermic temperature, heat flow-time curve or heat flow-temperature curve and pressure-time curve or pressure-temperature curve of the mixture.

[0097] If the pressure-time curve or the pressure-temperature curve of the mixture fluctuates, gas generation occurs, and a vacuum stability test is performed according to step S4.

[0098] If there is no gas generation, but the heat flow-time curve or the heat flow-temperature curve of the mixture fluctuates, heat release occurs, and a constant rate heating test is performed according to step S5.

[0099] If there is no gas generation and no heat release, the two chemicals are considered compatible.

[0100] S4. Conduct vacuum stability tests on chemicals and their mixtures.

[0101] A vacuum stability tester is used to test 0.1mg to 50g of two chemicals and their mixtures respectively. The test temperature is selected according to the heat and gas production screening test of the mixture of the two chemicals described in step S3. The temperature corresponding to the initial point of the pressure fluctuation in the pressure-time curve or pressure-temperature curve of the mixture obtained in step S3 is selected to be 10°C or higher, preferably between 40°C and 200°C. The experimental conditions such as the test quality and temperature of each chemical and its mixture are kept consistent. A pressure sensor is used to monitor the gas production in the warehouse. The test can be terminated when the pressure fluctuation is stable for more than 15 minutes. The gas production is converted from a pressure signal to an electrical signal, and the gas production volume is automatically calculated through the monitored temperature and pressure parameters.

[0102] The compatibility of the two chemicals can be evaluated by comparing the gas production volume of the two chemicals and their mixture or the pressure rise during the test process. If the gas production volume of the mixture is larger than the gas production volume of any one of the two chemicals, the two chemicals are judged to be Class C incompatible, and the compatibility classification is performed according to the increment of the unit gas production volume of the mixture compared to the unit gas production volume of the chemical with a lower unit gas production volume of the two chemicals; if the pressure rise during the test process of the mixture is larger than the unit pressure rise of any one of the two chemicals, the two chemicals are judged to be Class C incompatible, and the compatibility classification is performed according to the increment of the unit pressure rise of the mixture compared to the unit pressure rise of the chemical with a lower unit pressure rise of the two chemicals; otherwise, a constant rate heating test is performed according to step S5.

[0103] The C-level incompatibility is subdivided according to the gas production volume increment or pressure rise increment as shown in Table 8 and Table 9 below:

[0104] Table 8 Class C incompatibility classification based on gas production volume increment

[0105] Gas production volume increment (mL / g) Compatibility classification ＞20 C1 level incompatible 10～20 C2 level incompatibility 5～10 C3 level incompatibility 1～5 C4 level incompatibility ＜1 Compatible

[0106] Table 9 Class C incompatibility classification list based on pressure rise increment

[0107] Pressure rise increment (MPa / g) Compatibility classification ＞2 C1 level incompatible 2～5 C2 level incompatibility 0.5～2 C3 level incompatibility 0.1～0.5 C4 level incompatibility ＜0.1 Compatible

[0108] S5. Conduct constant rate temperature rise tests on chemicals and their mixtures.

[0109] Use a differential scanning calorimeter DSC, a microcalorimeter C80 or other equipment that meets the test requirements to test a certain amount of two chemicals and their mixtures. If the substance being tested is a volatile substance, it cannot be tested with an open device. The test mass is preferably 0.1mg~50g, the test heating rate is preferably 0.1~10℃ / s, the test starting temperature is the test temperature of the constant temperature heat generation test described in step S2, and the test maximum temperature is 400℃~600℃, or set according to the test needs.

[0110] The experimental conditions such as the test mass and temperature of the two chemicals and their mixture are kept consistent, and the test obtains the initial exothermic temperature, exothermic heat, exothermic peak and heat flow-time curve or heat flow-temperature curve of the two chemicals and their mixture under the test conditions.

[0111] Compare the initial exothermic temperature, exothermic heat, exothermic peak and heat flow-time curve or heat flow-temperature curve of the two chemicals and their mixture. If the initial exothermic temperature of the mixture under the test conditions is lower than the initial exothermic temperature of the two chemicals under the test conditions, the two chemicals are judged to be Class D incompatible, and the compatibility is graded according to the reduction in the measured initial exothermic temperature of the mixture under the test conditions compared with the one of the two chemicals with the lower initial exothermic temperature under the test conditions.

[0112] If the heat release of the mixture under the test conditions is higher than the heat release of both chemicals under the test conditions, the two chemicals are judged to be Class D incompatible, and the compatibility is graded based on the increase in the measured heat release of the mixture under the test conditions compared to the lower heat release of the two chemicals under the test conditions.

[0113] If the temperature corresponding to the heat flow peak of the mixture under the test conditions is lower than the temperatures corresponding to the heat flow peaks of the two chemicals under the test conditions, the two chemicals are judged to be D-level incompatible, and the compatibility is graded according to the amount of reduction in the temperature corresponding to the heat flow peak of the mixture under the test conditions compared to the temperature corresponding to the lower heat flow peak of the two chemicals under the test conditions.

[0114] If the heat flux peak heat generation power of the mixture under the test conditions is higher than the heat flux peak heat generation power of any one of the two chemicals under the test conditions, the two chemicals are judged to be D-level incompatible, and the compatibility is graded according to the increase in the heat flux peak heat generation power of the mixture under the test conditions compared to the chemical with the lower heat flux peak heat generation power under the test conditions; otherwise, the two chemicals are judged to be compatible.

[0115] The D-level incompatibility is subdivided according to the starting exothermic temperature reduction value or the heat release increase value or the temperature reduction value corresponding to the heat flux peak value or the heat flux peak heat generation power increase value as shown in the following Tables 10 to 13:

[0116] Table 10 D-level incompatibility classification based on the reduction in the starting exotherm temperature

[0117] Initial exothermic temperature drop (℃) Compatibility classification ＞10 D1 level incompatibility 10～50 D2 level incompatibility 5～10 D3-level incompatibility 2～5 D4-level incompatibility ＜2 Compatible

[0118] Table 11 D-level incompatibility classification based on heat release rise value

[0119] Heat release rise value (J / g) Compatibility classification ≥300 D1 level incompatibility 100～200 D2 level incompatibility 20～100 D3-level incompatibility 1～20 D4-level incompatibility ＜1 Compatible

[0120] Table 12 D-level incompatibility classification based on the temperature reduction value corresponding to the peak heat flux

[0121] Temperature drop corresponding to heat flow peak value (℃) Compatibility classification ＞10 D1 level incompatibility 10～50 D2 level incompatibility 5～10 D3-level incompatibility 2～5 D4-level incompatibility ＜2 Compatible

[0122] Table 13 D-level incompatibility classification list based on the peak heat flux heat generation power increase value

[0123] Peak heat flux and heat generation power increase value (mW) Compatibility classification ＞500 D1 level incompatibility 100～500 D2 level incompatibility 50～100 D3-level incompatibility 10～50 D4-level incompatibility ＜10 Compatible

[0124] The present invention tests the heat and gas generation phenomenon after the chemicals are mixed, as well as the difference in properties between the mixture and the original chemicals, and through logical judgment, clarifies the compatibility of the two, and divides the compatibility level, which solves the problem that most existing chemical compatibility assessment methods are based on the chemical composition and belonging category (such as acid, alkali, etc.) for judgment, and are not suitable for mixtures with unknown or complex components, which is of great significance to chemical management. The chemical compatibility test grading method provided by the present invention can be completed using only a small amount of chemicals, which is conducive to cost saving. The application prospects of the present invention are broad, and can be applied to the fields of compatibility research of chemicals with complex components, scientific and safe management of chemicals, risk assessment of chemical mixing, or hierarchical management of incompatible chemical groups based on compatibility classification.

[0125] The specific implementation of the present invention will be described in detail below in conjunction with specific embodiments and drawings.

[0126] Example 1

[0127] The compatibility between 10% hydrochloric acid solution and 1 mol / L sodium hydroxide solution is graded and tested by using the chemical compatibility test grading method provided by the present invention. The test uses a simple device, including a constant temperature device, a flask, a dropping funnel, a temperature measuring thermocouple and a pressure sensor.

[0128] Take 1ml of 10% hydrochloric acid solution and add it to the flask. Set the thermostat to 30℃. After the system temperature stabilizes at the set value for 10 minutes, take 1ml of 1mol / L sodium hydroxide solution and add it to the flask. At this time, the materials begin to mix, the temperature measuring thermocouple records the heat flow, and the pressure sensor records the pressure change in the flask.

[0129] After the experiment, the heat and gas production in the test were evaluated. After the two were mixed, there was obvious heat generation, and the heat release curve was as follows Figure 2 As shown. The two chemicals are judged to be incompatible at level A. In the test, the heat power generated by the two chemicals after mixing is 198mW. Further compatibility classification is performed and the two chemicals are incompatible at level A2.

[0130] Comparative Example 1

[0131] The compatibility between 10% hydrochloric acid solution and 1 mol / L sodium hydroxide solution was evaluated using the component analysis method. The components of 10% hydrochloric acid solution are hydrochloric acid and water, and the components of 1 mol / L sodium hydroxide solution are sodium hydroxide and water. Hydrochloric acid and sodium hydroxide react as follows at room temperature:

[0132] NaOH+HCl→NaCl+H2O

[0133] The reaction is irreversible, so 10% hydrochloric acid solution and 1 mol / L sodium hydroxide solution are incompatible.

[0134] Comparative Example 2

[0135] The compatibility between 10% hydrochloric acid solution and 1mol / L sodium hydroxide solution was evaluated using the property analysis method. 10% hydrochloric acid solution is acidic, and 1mol / L sodium hydroxide solution is alkaline. The two will undergo a neutralization reaction at room temperature. The reaction is exothermic and irreversible, so 10% hydrochloric acid solution and 1mol / L sodium hydroxide solution are incompatible.

[0136] Comparing Example 1 with Comparative Examples 1 and 2, the test conclusions of the three are consistent, which proves that the chemical compatibility test classification method provided by the present invention is effective. In addition, the present invention can obtain detailed classification conclusions.

[0137] Example 2

[0138] The compatibility between tar and light oil is graded by using the chemical compatibility test grading method provided by the present invention.

[0139] The test uses a simple device, including a thermostat, a flask, a dropping funnel, a temperature measuring thermocouple and a pressure sensor. Add tar to the flask, set the thermostat to 40°C, wait for the system temperature to stabilize at the set value for 10 minutes, then add 1 ml of light oil to the flask, and the materials begin to mix.

[0140] By monitoring the heat flow and system pressure, the heat and gas production of the system after the mixing begins are evaluated. The experiment found that the tar and light oil do not produce heat or gas after mixing. At this time, the test should continue according to step S2.

[0141] The C80 microcalorimeter was used to test the heat generation of tar, light oil and their mixture at a constant temperature. The test constant temperature was set to 50°C, 10°C higher than the S1 test temperature, and the test lasted for 48 hours. 1g of light oil, 1g of tar and 1g of their mixture were tested. Other experimental conditions remained the same, such as Figure 3 As shown, three heat flow-time curves at constant temperature were measured, and there was no fluctuation in the three heat flow-time curves, that is, the two chemicals and their mixtures did not release heat at constant temperature.

[0142] Adiabatic accelerating calorimeter was used to conduct heat and gas generation screening test on the mixture of tar and light oil. 1g of the mixture was weighed to start the test. The test starting temperature was 20℃. The HWS mode was used and the maximum test temperature was 450℃. The results are as follows: Figure 4 The mixture has an initial exothermic temperature of 86°C, an adiabatic temperature rise of 49°C, and a unit mass heat release of 677.763 J / g, indicating that heat generation occurs; an adiabatic pressure rise of 0.304 MPa, and a maximum pressure rise rate of 0.012 MPa / min, indicating that gas generation occurs. A vacuum stability test is performed according to step S4.

[0143] The vacuum stability tester was used to test the two chemicals and their mixtures respectively. The test temperature was 100°C. The test conditions such as the test quality and temperature of each chemical and its mixture were kept consistent. The pressure sensor was used to monitor the gas production in the chamber. If the pressure fluctuation temperature exceeded 15 minutes, the test was terminated. The gas production was converted from a pressure signal to an electrical signal. The pressure rise increment was automatically calculated through the monitored temperature and pressure parameters, as shown in Table 14:

[0144] Table 14 Unit mass pressure rise of test samples

[0145]

[0146]

[0147] It can be seen from Table 14 that the pressure rise increments are:

[0148] The pressure increase of the mixture of tar and light oil compared with tar is: 0.376-0.292=0.084MPa / g

[0149] The pressure increase of the mixture of tar and light oil compared with light oil is: 0.376-0.314=0.062MPa / g

[0150] The pressure increase increments are all less than 0.1 MPa / g, and the constant rate heating test is continued according to step S5.

[0151] The tar, light oil and their mixture were tested using a microcalorimeter C80. The tested substances are volatile and cannot be tested with open equipment. The test starting temperature is 25°C, the test maximum temperature is 300°C, the heating rate is 2°C / min, and 1g of light oil, 1g of tar and 1g of the mixture of the two are taken for testing. Other experimental conditions are kept consistent, such as Figure 5 As shown, the test obtains the starting exothermic temperature, exothermic amount, exothermic peak value, and heat flow-temperature curve of the two chemicals and their mixture under the test conditions.

[0152] Depend on Figure 5 It can be seen that the initial exothermic temperature of the mixture under the test conditions is lower than that of the tar under the test conditions, but the initial exothermic temperature of the lighter oil under the test conditions is higher, and the two chemicals are compatible.

[0153] Under the test conditions, the temperature corresponding to the heat flow peak of the mixture is lower than that of the tar under the test conditions, but the temperature corresponding to the heat flow peak of the lighter oil under the test conditions is higher, and the two chemicals are compatible.

[0154] The heat flux peak heat generation power of the mixture under the test conditions is higher than that of the light oil under the test conditions, but lower than that of the tar under the test conditions, and the two chemicals are compatible.

[0155] Comparative Example 3

[0156] The compatibility between tar and light oil was evaluated using component analysis methods.

[0157] The main components of light oil are alkanes, cycloalkanes or aromatic hydrocarbons with 5-11 carbon atoms; the main components of tar are various aromatic hydrocarbon compounds such as benzene, toluene, xylene, naphthalene, benzopyrene, benzopyrene phenol, etc. According to the analysis of the main components, the two are compatible.

[0158] Comparing Example 2 with Comparative Example 3, the compatibility analysis conclusions of the two are consistent. Tar and light oil have complex components, and it is not possible to fully know all the components, so the component analysis method is incomplete. The present invention evaluates compatibility through experimental conclusions, which is more authentic and reliable, and can obtain detailed classification conclusions.

[0159] Example 3

[0160] The compatibility between styrene tar and iron oxide is graded and tested by using the chemical compatibility test grading method provided by the present invention.

[0161] The test uses a simple device, including a thermostat, a flask, a funnel, a temperature measuring thermocouple and a pressure sensor. 2g of tar is added to the flask, and the temperature of the thermostat is set to 20℃. After the system temperature stabilizes at the set value for 10 minutes, 2g of Fe2O3 is added to the flask, and the materials begin to mix.

[0162] By monitoring the heat flow and system pressure, the heat and gas production of the system after the mixing begins are evaluated. The experiment found that styrene tar and iron oxide do not produce heat or gas after mixing. At this time, the test should be carried out according to step S2.

[0163] Differential scanning calorimeter DSC was used to conduct constant temperature heat generation tests on styrene tar, iron oxide and their mixture. The test constant temperature was set at 70°C and the test time was 20 hours. 50 mg of styrene tar, 50 mg of iron oxide and 50 mg of the mixture of the two were taken for testing, and other experimental conditions remained the same.

[0164] like Figure 6 As shown, three heat flow-time curves were measured at constant temperature. Comparing the three heat flow-time curves, styrene tar and iron oxide did not generate heat at 70℃ for 20h, while the mixture of styrene tar and iron oxide generated heat, and the two were Class B incompatible. Further grading evaluation showed that the peak heat generation power increase value of heat flow was 85mW, which was Class B3 incompatible.

[0165] Comparative Example 4

[0166] The compatibility between styrene tar and iron oxide was evaluated using a compositional analysis method.

[0167] The main component of styrene tar is styrene, which has a certain reducing property and can be oxidized to styrene oxide and benzaldehyde. Iron oxide has a certain oxidizing property. The two will undergo a redox reaction and are therefore incompatible.

[0168] Comparing Example 3 with Comparative Example 4, the compatibility analysis conclusions of the two are consistent. The present invention evaluates compatibility through experimental conclusions, the conclusions are true and reliable, and detailed classification conclusions can be obtained.

[0169] Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by technicians in this technical field within the essential scope of the present invention should also fall within the protection scope of the present invention.

Claims

1. A chemical compatibility test and grading method, characterized in that: The following steps are involved: S1. Conduct chemical mixing test; Take appropriate amounts of two chemicals and place them in the test container. At this time, the two chemicals do not touch each other. After the system temperature stabilizes at the set value, mix the two chemicals. By monitoring the heat flow and system pressure or the change in the quality of the chemicals before and after the test, the heat generation, gas generation and reaction conditions of the system after the mixing begins are evaluated. If there is a certain amount of heat generation, gas generation or a change in the quality of the chemicals before and after the test after the two chemicals are mixed, it is determined that the two chemicals are Class A incompatible, and the compatibility is graded according to the heat generation, gas generation or the degree of change in the quality of the chemicals before and after the test. The evaluation is completed. If the two chemicals do not generate heat or gas after mixing, the change in the quality of the chemicals before and after the test is not considered at this time, and the test is continued according to step S2; S2. Conduct constant temperature heat generation test on chemicals and their mixtures; A constant temperature heat generation test was performed on a certain amount of two chemicals and their mixture. The test mass of the two chemicals and the test mass of their mixture as well as the temperature and other experimental conditions were kept consistent. Three heat flow-time curves under constant temperature were measured. If the unit heat generation of the mixture is greater than that of any of the two chemicals and the increment is ≥1J / g, the two chemicals are judged to be Class B incompatible, and the compatibility is graded according to the measured unit heat generation; if the peak heat generation power of the heat flux of the mixture is greater than that of any of the two chemicals and the increment is ≥10mW, the two chemicals are judged to be Class B incompatible, and the compatibility is graded according to the measured peak heat generation power of the heat flux; Otherwise, follow-up testing should be conducted; S3. Conducting a heat and gas generation screening test on a mixture of two chemicals; Conducting a heat and gas generation screening test on a mixture of two chemicals to obtain the starting exothermic temperature, heat flow-time curve or heat flow-temperature curve and pressure-time curve or pressure-temperature curve of the mixture; If the pressure-time curve or the pressure-temperature curve of the mixture fluctuates, gas generation occurs, and a vacuum stability test is performed according to step S4; If there is no gas generation, but the heat flow-time curve or the heat flow-temperature curve of the mixture fluctuates, then there is heat release, and a constant rate heating test is performed according to step S5; If there is no gas generation and no heat release, the two chemicals are considered compatible; S4. Conduct vacuum stability tests on chemicals and their mixtures; A certain amount of two chemicals and their mixtures are tested respectively. The test quality and temperature of each chemical and its mixture are kept consistent. The gas production in the chamber is monitored. The test can be terminated when the pressure fluctuation is stable for a period of time. The gas production volume is automatically calculated based on the monitored temperature and pressure parameters. Compare the gas production volumes of the two chemicals and their mixtures or the pressure rise during the test process. If the gas production volume of the mixture is larger than the gas production volume of any one of the two chemicals, the two chemicals are determined to be Class C incompatible, and the compatibility classification is performed according to the increment of the unit gas production volume of the mixture compared to the unit gas production volume of the chemical with a lower unit gas production volume of the two chemicals; if the pressure rise during the test process of the mixture is larger than the unit pressure rise of any one of the two chemicals, the two chemicals are determined to be Class C incompatible, and the compatibility classification is performed according to the increment of the unit pressure rise of the mixture compared to the unit pressure rise of the chemical with a lower unit pressure rise of the two chemicals; otherwise, perform a constant rate temperature rise test according to step S5; S5. Conduct constant rate heating test on chemicals and their mixtures; A certain amount of two chemicals and their mixture are tested respectively, and the experimental conditions such as the test mass and temperature of the two chemicals and their mixture are kept consistent, and the test obtains the initial exothermic temperature, the amount of exothermic heat, the exothermic peak value and the heat flow-time curve or the heat flow-temperature curve of the two chemicals and their mixture under the test conditions; Compare the initial exothermic temperature, exothermic heat, exothermic peak and heat flow-time curve or heat flow-temperature curve of the two chemicals and their mixture. If the initial exothermic temperature of the mixture under the test conditions is lower than the initial exothermic temperature of the two chemicals under the test conditions, the two chemicals are judged to be Class D incompatible, and the compatibility classification is performed according to the reduction of the initial exothermic temperature of the mixture under the test conditions compared with the lower initial exothermic temperature of the two chemicals under the test conditions; If the heat release of the mixture under the test conditions is higher than the heat release of both chemicals under the test conditions, the two chemicals are judged to be Class D incompatible, and the compatibility classification is performed based on the increase in the heat release of the mixture under the test conditions compared to the lower heat release of the two chemicals under the test conditions; If the temperature corresponding to the heat flow peak value of the mixture under the test conditions is lower than the temperature corresponding to the heat flow peak value of the two chemicals under the test conditions, the two chemicals are judged to be D-level incompatible, and the compatibility classification is performed according to the reduction in the measured temperature corresponding to the heat flow peak value of the mixture under the test conditions compared with the temperature corresponding to the lower heat flow peak value of the two chemicals under the test conditions; If the heat flux peak heat generating power of the mixture under the test conditions is higher than the heat flux peak heat generating power of any of the two chemicals under the test conditions, the two chemicals are judged to be D-level incompatible, and the compatibility is graded according to the increase in the heat flux peak heat generating power of the mixture under the test conditions compared with the lower heat flux peak heat generating power of the two chemicals under the test conditions; Otherwise, the two chemicals are judged to be compatible.

2. The chemical compatibility testing and grading method according to claim 1, characterized in that: The test mass of the chemical in step S1 is 0.1 mg to 50 g, the test container is a constant temperature closed reaction box, and the test temperature is about 10°C higher than the actual working environment temperature. If there is no reference temperature, the constant temperature is set between 40°C and 100°C, or is set according to test needs.

3. The chemical compatibility testing and grading method according to claim 2, characterized in that: In step S2, a calorimetric device is used for testing, the test mass is 0.1 mg to 50 g, the test temperature is about 10° C. to 50° C. higher than the test temperature in step S1, and the test time is 4 to 48 hours, which can also be set according to test needs.

4. The chemical compatibility testing and grading method according to claim 3, characterized in that: In step S3, a rapid screening calorimeter or an adiabatic accelerating calorimeter is used for testing, the test starting temperature is the test temperature of the constant temperature heat generation test in step S2, the test maximum temperature is 400°C to 600°C, and the test mass of the mixture of the two chemicals is 0.1mg to 50g.

5. The chemical compatibility testing and grading method according to claim 4, characterized in that: In step S4, a vacuum stability tester is used for testing, and the test temperature is selected to be 10° C. higher than the temperature corresponding to the initial point of the pressure fluctuation in the pressure-time curve or the pressure-temperature curve of the mixture obtained in step S3 according to the heat and gas generation screening test of the mixture of the two chemicals described in step S3; The test mass is 0.1 mg to 50 g, and the test temperature is between 40° C. and 200° C.

6. The chemical compatibility testing and grading method according to claim 5, characterized in that: In step S5, a calorimetric device is used for testing, the test starting temperature is the test temperature of the constant temperature heat generation test in step S2, and the test maximum temperature is 400° C. to 600° C., or is set according to the test requirements; The test mass is 0.1 mg to 50 g, and the test heating rate is 0.1 to 10° C. / s.

7. The chemical compatibility testing and grading method according to any one of claims 1 to 6, characterized in that: The Class A incompatibility is subdivided according to the amount of heat or gas produced or the degree of change in the quality of the chemical before and after the test as follows:

8. The chemical compatibility testing and grading method according to claim 7, characterized in that: The Class B incompatibility is subdivided according to the heat generation increment or the heat flux peak heat generation power increase value as follows:

9. The chemical compatibility testing and grading method according to claim 8, characterized in that: The Class C incompatibility is subdivided according to the gas production volume increment or pressure rise increment as follows:

10. The chemical compatibility testing and grading method according to claim 9, characterized in that: The D-level incompatibility is subdivided according to the starting exothermic temperature reduction value or the heat release increase value or the temperature reduction value corresponding to the heat flux peak value or the heat flux peak heat generation power increase value as follows:

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