CN113552109B - Memory, and method, device and equipment for testing and analyzing reaction thermal effect based on Raman spectrum - Google Patents
Memory, and method, device and equipment for testing and analyzing reaction thermal effect based on Raman spectrum Download PDFInfo
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Abstract
The invention discloses a reaction thermal effect test analysis method based on Raman spectrum, which comprises the following steps: in the slow chemical reaction or low exothermic load chemical reaction process, synchronously performing a reaction calorimetric test and an in-situ Raman spectrum test; generating a curve from the change data of the active functional groups read by the in-situ Raman spectrum test, wherein the curve is used as a calibration standard of a calorimetric curve; and carrying out dynamic optimization matching on a heat accumulation curve obtained through the reaction calorimetric test relative to the change curve of the active functional group, so as to obtain a reaction heat effect curve through integration. The invention aims at the slow exothermic chemical reaction or the low exothermic load chemical reaction, and can effectively improve the true reliability of the reaction heat data.
Description
Technical Field
The invention relates to a thermal effect data processing method for a reaction calorimetric test in the petrochemical field, in particular to a memory, a reaction thermal effect test analysis method, a device and equipment based on Raman spectrum.
Background
Most chemical reactions in chemical processes are exothermic reactions, during which energy is released, and in the event of an accident, the amount of energy released is directly related to the potential loss. Thus, the heat of reaction is a key data therein and is also an important basis for assessing the operational risk of industrial devices. The thermal runaway risk analysis is carried out on a specific process, parameters such as the heat release rate, the heat release amount, the adiabatic temperature rise, the adiabatic pressure rise and the like of the reaction are required to be obtained, the parameters are usually required to be obtained through testing by a reaction calorimeter, the thermodynamic analysis software is adopted to integrate basic heat release power data measured by the instrument, a basic reaction thermal effect diagram is obtained, and the thermodynamic effect diagram is analyzed by the software to obtain relevant thermodynamic parameters. For example, the single-step runaway reaction is usually based on the result of a linear temperature rise test, and a single-curve model fitting method is adopted to obtain data such as activation energy, factor before finger and the like; for complex multi-step reaction, the testing curve is solved by adopting an Ozawa-Flynn-Wall conversion rate or Friedman conversion rate model-free algorithm in a judgment step combination mode, so that basic data information for risk assessment is obtained. For example, bezier, linear, tangential methods, etc. are used.
The conventional reaction calorimeter mainly comprises an RC1 reaction calorimeter of Metretolidol company, a VSP2 adiabatic calorimeter of FAI company in the United states, a DSC differential scanning calorimeter of a relaxation-resistant company and the like, wherein the exothermic power curve of a reaction system is obtained by monitoring the change of heat flow information of a test sample in real time in the test process, the exothermic power curve is processed by adopting a mathematical integration method carried by the system, a reaction heat effect diagram can be obtained, and thermodynamic solution is carried out, so that data support is provided for risk evaluation.
The existing instrument and equipment and analysis method still have certain limitations, have good suitability for reactions which are violent in thermal effect and fast to carry out, and if the exothermic power intensity is 10W and the baseline deviation is 0.1W, the error obtained by integrating the reaction heat is about 1%. However, when the reaction system belongs to a slow exothermic chemical reaction, such as liquid phase hydrogenation, liquid phase oxidation, esterification, etherification, etc., the exothermic power of the reaction thermal zone is usually 0.1W, if the baseline deviation is also 0.1W, the thermal effect curve obtained through the test of the reaction calorimeter will be closely attached to the balance calibration baseline, because the subjectivity to the baseline calibration is larger when the existing analysis software processes data, the weak integral baseline deviation can cause the double change of the exothermic power, the reaction test time is usually longer, up to several hours, the tiny exothermic power deviation can cause very large reaction thermal deviation when the exothermic power integrates the time to obtain the reaction heat, the obtained data cannot accurately classify the reaction risk, and the corresponding safety control standard is guided to be established. Similarly, chemical reactions with low exothermic loads, such as esterification, etherification, superposition, etc., can also cause large deviations in the heat of reaction when tested using the aforementioned prior instrumentation and analytical methods.
In the currently published literature patent, for example, the Chinese patent application CN101603935A tests the exothermic effect with high sensitivity by strengthening a sensor and optimizing a control mode, and adopts a conventional integral method for the subsequent calorimetric treatment, and has no scientific and unified standard and method for guiding the treatment of calorimetric data.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a method for testing and analyzing reaction heat data obtained by a slow exothermic chemical reaction or a low exothermic load chemical reaction, which can effectively improve the true reliability of the reaction heat data.
To achieve the above object, according to a first aspect of the present invention, there is provided a thermal effect test analysis method for reaction based on raman spectroscopy, comprising the steps of: in the slow chemical reaction or low exothermic load chemical reaction process, synchronously performing a reaction calorimetric test and an in-situ Raman spectrum test; generating a curve from the change data of the active functional groups read by the in-situ Raman spectrum test, wherein the curve is used as a calibration standard of a calorimetric curve; and carrying out dynamic optimization matching on a heat accumulation curve obtained through the reaction calorimetric test relative to the change curve of the active functional group, so as to obtain a reaction heat effect curve through integration.
Further, in the above technical solution, before the synchronous test, the method further includes: and measuring the spectrogram of each reactant in the slow chemical reaction process or the low exothermic load chemical reaction process, and marking the characteristic peak of the active functional group which possibly reacts.
Further, in the above technical solution, the heat accumulation curve may be obtained by: the exothermic power curve obtained by the calorimetric test is converted into a heat accumulation curve.
Further, in the above technical solution, the reactive functional groups that may react during the slow chemical reaction include: a carbon-carbon double bond, a carbon-carbon triple bond, an azo bond, or a peroxy bond; the reactants in the slow chemical reaction process are organic matters or inorganic matters; the reaction system is an organic system, a water system or an oil-water mixed system.
Furthermore, in the technical scheme, the raman spectrometer is arranged outside the reaction kettle, the reaction kettle can be a glass kettle, a quartz kettle or a reaction kettle made of metal materials, and a transparent window is arranged on the reaction kettle.
Further, in the above technical scheme, the reaction progress of the slow chemical reaction or the low exothermic load chemical reaction is monitored by the change trend of the active functional group.
In the technical scheme, the step of generating the curve by using the change data of the active functional group read by the in-situ Raman spectrum test specifically comprises the following steps: and carrying out normalization processing on the change data of the characteristic peak intensity of the active functional group, which is read by the in-situ Raman spectrum test, along with time, so as to generate a Raman basic thermal analysis standard curve.
Further, in the above technical solution, the process of obtaining the heat accumulation curve specifically includes: the exothermic power curve obtained by the calorimetric test is given a baseline initial value and is integrated and converted into a heat accumulation curve.
Further, in the above technical solution, the integration method of the integration-to-heat accumulation curve may be specifically a dynamic bezier method, a tangent method or a linear method.
Further, in the above technical solution, the dynamic optimization matching may specifically be: two lever lines are arranged at the starting point of integration, and the heat release accumulation curve is obtained through slope optimization of the lever lines, so that the heat release accumulation curve is consistent with the Raman basic thermal analysis standard curve.
According to a second aspect of the present invention, there is also provided a raman spectrum-based thermal reaction effect test analysis apparatus for thermal reaction effect testing of a slow chemical reaction process or a low exothermic load chemical reaction process, comprising: the functional group change curve generating unit is used for generating a curve from the active functional group change data read by the in-situ Raman spectrum test and taking the curve as a calibration standard of the calorimetric curve; the heat accumulation curve conversion unit is used for converting the exothermic power curve obtained by the reaction heat test into a heat accumulation curve; and the optimizing and matching unit is used for dynamically optimizing and matching the heat accumulation curve relative to the change curve of the active functional group so as to integrate and obtain a reaction heat effect curve.
Further, in the above technical solution, the method further includes: and a measuring and marking unit for measuring the spectrogram of each reactant in the slow chemical reaction process or the low exothermic load chemical reaction process and marking the characteristic peak of the active functional group possibly occurring in the reaction.
In the above technical solution, the functional group change curve generating unit may further include a normalization processing subunit, configured to normalize the change data of the active functional group characteristic peak intensity read by the in-situ raman spectrum test over time.
In the above technical solution, the heat accumulation curve conversion unit may further include an integration unit, configured to assign a baseline initial value to the exothermic power curve obtained by the calorimetric test and integrate the baseline initial value.
In the above technical solution, the optimizing and matching unit may further include a slope adjusting subunit, configured to set two lever lines at the integration starting point, and obtain the heat accumulation curve by adjusting the slope of the lever lines.
According to a third aspect of the present invention there is also provided a memory comprising a set of instructions adapted to cause a processor to perform the steps of any of the aforementioned raman spectrum based methods of testing analysis of thermal effects of reactions.
According to a fourth aspect of the present invention, the present invention also provides a thermal reaction effect test analysis device based on raman spectrum, comprising a bus, an input device, an output device, a processor and the aforementioned memory; the bus is used for connecting the memory, the input device, the output device and the processor; the input device and the output device are used for realizing interaction with a user; the processor is configured to execute the set of instructions in the memory.
Compared with the prior art, the invention has the following beneficial effects:
1. by arranging a Raman spectrometer outside the reaction calorimeter, the change rule of the active functional group can be measured in real time in the reaction calorimeter process;
2. the heat integration baseline is optimized by adjusting the matching degree of the functional group and the heat accumulation curve, so that the reaction heat is accurately obtained;
3. the Raman spectrum-based test can be applied to nonpolar groups, water-containing samples or inorganic substances, and has a characteristic section of 40-4000cm -1 。
Other features and aspects of the present invention will become apparent from the following detailed description of exemplary embodiments, which proceeds with reference to the accompanying drawings.
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, in which like references indicate similar elements, and in which the figures of the drawings are not to be taken in a limiting sense, unless otherwise indicated.
Fig. 1 is a schematic step diagram of a raman spectrum-based reaction thermal effect test analysis method according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a thermal effect testing and analyzing device based on raman spectrum according to an embodiment of the present invention;
fig. 3 is a schematic hardware structure diagram of a reaction thermal effect test analysis device based on raman spectrum according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of integrating the exothermic power curve using Bessel method in accordance with an embodiment of the present invention;
FIG. 5 is a schematic diagram of the adjustment and optimization of the integral baseline by Bessel method according to the embodiment of the invention;
FIG. 6 is a graph showing the judgment of the matching degree of the heat accumulation curve and the active functional group change curve according to the embodiment of the invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some instances, well known methods, procedures, and components have not been described in detail so as not to obscure the present invention.
Example 1
The method for testing and analyzing the reaction heat effect of the slow chemical reaction process or the low exothermic load chemical reaction process comprises the following steps:
and S11, measuring a spectrum chart of each reactant in the slow chemical reaction process or the low exothermic load chemical reaction process, and marking the characteristic peak of the active functional group possibly reacted. Specifically, an in-situ Raman spectrometer is adopted to measure the spectrograms of all reactants, a Raman characteristic spectrum library of a reaction system is established, characteristic peaks of active functional groups which possibly react are recorded for marking, and the marking of the characteristic peaks can refer to the existing Raman spectrum analysis method. Further, for the slow chemical reaction process, the structural characteristics of the reactants are focused on the positions of characteristic peaks of functional groups such as carbon-carbon double bonds, carbon-carbon triple bonds, azo bonds, peroxy bonds and the like in a Raman spectrum spectrogram, and characteristic peaks with very high intensity in the products can be selected as tracking peaks. The reactants in the slow chemical reaction process can be organic matters or inorganic matters; the reaction system can be an organic system, a water system or an oil-water mixed system.
Step S12, synchronously performing a reaction calorimetric test and an in-situ Raman spectrum test in a slow chemical reaction process or a low-exothermic load chemical reaction process; by adding the Raman spectrometer outside the reaction kettle of the reaction calorimeter, the reaction kettle can be a glass kettle, a quartz kettle or a reaction kettle made of metal materials, and a transparent window is arranged on the reaction kettle so as to facilitate the transmission of a light source. In the test process, the Raman spectrometer is tested through the transparent window, so that the combined test of the reaction calorimeter and the in-situ Raman spectrometer can be realized, and the thermal effect data and the real-time in-situ Raman dynamic spectrum of the reaction system can be tested. Preferably, but not limited to, the change trend of the active functional group marked in step S11 is focused in the test process, and is used as a monitoring index of the reaction progress, when the characteristic functional group is not changed any more, the reaction is considered to be finished, and an exothermic power curve and a dynamic raman spectrum are obtained after the test is finished.
And S13, generating a curve from the change data of the active functional groups read by the in-situ Raman spectrum test. Specifically, the change data of the characteristic peak intensity of the active functional group along with time is extracted from dynamic Raman spectrum data, and the peak intensity value is normalized, wherein the normalization treatment means that the peak intensity is different for different substances, the range is 0-3000, the range is 0-500, the peak intensity of different substances is processed to be 0-100%, and the comparison with a thermal conversion rate curve (the ordinate range of the thermal conversion rate is 0-100%) can be more conveniently carried out, so that a Raman basic thermal analysis standard curve is generated, and the curve is used as a calibration standard of a calorimetric curve.
Step S14, converting the exothermic power curve obtained by the reaction heat test into a heat accumulation curve. Specifically, a base line initial value is given to the exothermic power curve measured by the reaction calorimeter, and a Bessel, linear, tangential and other mathematical integration method can be adopted to perform primary integration treatment on the exothermic power curve to obtain the total reaction heat Q of the system Total (S) And a reaction heat integral Q within a range from the reaction start point to a certain time point t t Real-time Q t And Q is equal to Total (S) The ratio of (2) can be converted into a heat accumulation curve. If a tangent method is adopted, the base line setting mode of the tangent method can adopt a mode of y=kx+b, and no other special requirements exist. If a linear method is adopted, the baseline setting mode of the linear method adopts a form of y=b, and no other special requirements exist. If Bessel method is adopted, firstly, exothermic power curve of the reaction system is read (as shown in figure 4 a), and the basic principle of base line setting of Bessel method is as shown in figure 4b and P 0 、P 0 2 、P 2 Is a parabola with three different points sequentially passing through P 0 And P 2 Two tangents to the point intersect at P 1 Point at P 0 2 Tangent line intersection P of points 0 P 1 And P 2 P 1 At P 0 1 And P 1 1 The expression is as follows:
when P 0 ，P 2 Fixing, introducing a parameter t, and enabling the ratio to be t (1-t), namely:
and by analogy, increasing the number of data points to form a recurrence formula of the Bessel baseline:
where k=1, 2, … n; i=0, 1, … n-k
The exothermic amount of the reaction system was obtained by integrating the exothermic power curve through the base line, i.e., a heat accumulation curve was obtained (see fig. 4 c).
And S15, carrying out dynamic optimization matching on the heat accumulation curve relative to the change curve of the active functional group, and thus obtaining a reaction heat effect curve through integration. Specifically, the heat accumulation curve and the characteristic functional group change curve are compared, the integral baseline is adjusted and optimized, the baseline adjusting method can adopt a Bezier method, a linear method, a tangent method and the like, two initial lever lines can be arranged at the integral starting point by taking the Bezier method as an example, corresponding heat effect integral data and a heat accumulation curve are obtained by adjusting the slope optimization of the lever lines (the two lever lines refer to fig. 5a and 5b respectively), and the heat accumulation curve is consistent with the raman basic thermal analysis standard curve obtained in the step S13. The optimization process of the integration methods such as the linear method, the tangent method and the like in the data processing process is similar. When the heat accumulation curve and the active functional group change curve have the highest matching degree, the characteristic baseline is extracted to be the integral basis of calorimetric integration, and the characteristic baseline is the heat integral curve, and when the characteristic baseline is the baseline, the obtained heat conversion rate curve is consistent with the trend of the Raman characteristic line, as shown in figure 6. The obtained reaction heat and heat release power curve is a real thermal effect curve, and can be used for subsequent thermal dynamics parameter treatment of reaction runaway.
Example 2
This example illustrates a specific slow chemical reaction, a test analysis method of the present invention. The liquid phase hydrogenation reaction of benzene to prepare cyclohexane is a typical slow chemical reaction, and is influenced by gas-liquid-solid mass transfer, and the reaction rate is very low. In this example, a 2L RC1 reactor was used for calorimetric testing. The test mode can be a Tr mode, the temperature in the reaction kettle is maintained to be a constant value in the test process, and when the exothermic reaction temperature in the reaction kettle is increased, a cold source of a jacket is adjusted, and the reaction heat is removed, so that the temperature returns to an initial value; tj mode can also be selected, the temperature of the cold source of the jacket of the reaction kettle is maintained to be a constant value, and the heat generated by exothermic reaction in the reaction kettle is removed by the constant-temperature cold source. The change of the internal active functional group is monitored in real time outside the reaction kettle by using a Raman spectrometer. Reaction information: 140g of benzene, 500g of water and 20g of solid catalyst, wherein the reaction temperature is 145 ℃, the pressure of a hydrogen maintaining system is 40bar, and the reaction time is 4 hours. According to exothermic power data read by a reaction system, the conventional Bezier integration method, the conventional triangular curve integration method, the conventional exothermic starting point horizontal tangent method and the conventional exothermic end point horizontal tangent method are respectively adopted to process the calorimetric data, and the reaction heat is 439kJ, 172kJ, 876kJ and-4 kJ respectively. Different processing methods can have very large errors.
According to the spectrogram of Raman standard spectrum, 800cm -1 As the cyclic respiration peak of the cyclohexane, the peak gradually decreases with time during the test, and the actual progress of the reaction is characterized by subjecting it to a reverse conversion treatment (100% -relative intensity%) during the data processing. The reverse conversion treatment comprises the following steps: the intensity of the peak at which no hydrogenation reaction initially occurs was tested to be 100%, which was obtained by 100% -100% (test value) treatment, and the heat accumulation conversion was practically 0%; when the peak intensity is reduced to 80%, the actual progress is 100% -80%, and the heat accumulation conversion rate is 20%; when the peak intensity is completely disappeared, the actual progress is 100% -0, and the heat accumulation conversion rate is 100%. Integrating the different methodsAnd comparing the obtained heat accumulation curve with a Raman characteristic peak, wherein the heat conversion accumulation curve obtained by integrating by the second method is basically consistent with the characteristic functional group change trend. From this, it was confirmed that the reaction heat of the benzene hydrogenation process in the examples was 172kJ.
Example 3
This example illustrates another specific slow chemical reaction, the test analysis method of the present invention. The acetic acid and cyclohexene esterification process should be a typical slow chemical reaction. In this example, a 2L RC1 reactor was used for calorimetric testing. The test mode can be a Tr mode, the temperature in the reaction kettle is maintained to be a constant value in the test process, and when the exothermic reaction temperature in the reaction kettle is increased, a cold source of a jacket is adjusted, and the reaction heat is removed, so that the temperature returns to an initial value; tj mode can also be selected, the temperature of the cold source of the jacket of the reaction kettle is maintained to be a constant value, and the heat generated by exothermic reaction in the reaction kettle is removed by the constant-temperature cold source. The change of the internal active functional group is monitored in real time outside the reaction kettle by using a Raman spectrometer. Reaction information: 300g of acetic acid, 410g of cyclohexene, 200g of solution water, 40g of acid resin catalyst, the reaction temperature is 80 ℃, the nitrogen maintains the system pressure of 5bar, and the reaction time is 6 hours. According to exothermic power data read by a reaction system, the conventional triangle curve integration method, the exothermic starting point horizontal tangent integration method and the exothermic end point horizontal tangent integration method are respectively adopted to process the calorimetric data, and the reaction heat is 355kJ, 754kJ and 1400kJ respectively. Different processing methods can have very large errors.
2880cm from the spectrum of the Raman standard spectrum -1 Is a characteristic peak of the ester group-COO-of the cyclohexyl acetate, the peak is gradually increased as the reaction proceeds in the test process, and the peak intensity is normalized to 100% in the test time range; the reaction was completed when the peak intensity did not change. And comparing the heat accumulation curve obtained by the different integration methods with the Raman characteristic peak, wherein the heat conversion accumulation curve obtained by the second integration method is basically consistent with the characteristic functional group change trend. From this, it was confirmed that the reaction heat during the esterification reaction in the examples was 744kJ. During the test, it was found thatAfter 4 hours, the characteristic peak of the ester group is not increased, which indicates that the reaction system reaches equilibrium, and in the actual production process, if the batch method is adopted to produce the cyclohexyl acetate, although the reaction rate is very slow, the reaction time is not required to be increased limitlessly, so that the yield is improved. The equilibrium conversion of cyclohexene was found to be 65% by chromatography, which could be converted to 229kJ/mol for the heat of esterification, which was very close to 242kJ/mol for the theoretical calculation of the heat of esterification.
Example 4
This example illustrates a specific low exothermic load chemical reaction, a test analysis method of the present invention. Acetic acid, ethanol esterification reactions are typically low exothermic load reactions, equilibrium reactions, very low heat of reaction, about 25kJ/mol. In this example, a calorimetric test was performed using a 5L RC1 reactor in Tr mode, and the change in active functional groups was monitored in real time through a transparent quartz glass wall using a raman spectrometer. Reaction information: 1.5kg of acetic acid and 1.2kg of ethanol, wherein the reaction temperature is 110 ℃, the pressure is 5bar, and the reaction time is 6 hours. According to exothermic power data read by a reaction system, a Bessel integration method, an exothermic start point horizontal tangent method, an exothermic end point horizontal tangent method and an average method are respectively adopted to process the calorimetric data, and the reaction heat is 449kJ, 717kJ, 363kJ and 97kJ respectively. Different processing methods can have very large errors.
Since the characteristic peak of raman spectrum c=o of ethyl acetate is 2492cm -1 And the change trend of the characteristic functional groups in the reaction process is read by a Raman spectrometer, and the thermal conversion cumulative curve is obtained through integration by a first method and is basically consistent with the change trend of the characteristic functional groups through data comparison. From this, it was confirmed that the reaction heat of acetic acid and ethanol in this example was 449kJ.
Example 5
As shown in fig. 2, the thermal effect test analysis device based on raman spectrum of the present embodiment is a device corresponding to the test analysis method in embodiment 1, that is, the method in embodiment 1 is implemented by means of a virtual device, and each virtual module constituting the thermal effect test analysis device based on slow chemical reaction process or low exothermic load chemical reaction process of raman spectrum may be executed by an electronic apparatus, such as a network device, a terminal device, or a server.
The reaction thermal effect test analysis device based on raman spectrum provided in this embodiment specifically includes: a measuring and marking unit 1, a functional group change curve generating unit 2, a heat accumulation curve converting unit 3 and an optimizing and matching unit 4. The measuring and marking unit 1 is used for measuring the spectrogram of each reactant in the slow chemical reaction process or the low exothermic load chemical reaction process and marking the characteristic peak of the active functional group which possibly reacts; the functional group change curve generating unit 2 is used for generating a curve from the active functional group change data read by the in-situ Raman test, and taking the curve as a calibration standard of a calorimetric curve; the heat accumulation curve conversion unit 3 is used for converting an exothermic power curve obtained by the reaction heat test into a heat accumulation curve; the optimizing and matching unit 4 is used for dynamically optimizing and matching the heat accumulation curve relative to the reactive functional group change curve, so that the reaction heat effect curve is obtained through integration.
Example 6
The present embodiment provides a memory, which may be a non-transitory (non-volatile) computer storage medium storing computer executable instructions that can execute the steps of the raman spectrum-based reaction thermal effect test analysis method in any of the above method embodiments, and achieve the same technical effects.
Example 7
The embodiment provides a thermal effect test analysis device based on raman spectroscopy, which comprises a memory, wherein the memory comprises a corresponding computer program product, and when program instructions contained in the computer program product are executed by a computer, the computer can execute the thermal effect test analysis method in each aspect and realize the same technical effects.
Fig. 3 is a schematic diagram of the hardware structure of the electronic device according to this embodiment, and as shown in fig. 3, the device includes one or more processors 610 and a memory 620. Take one processor 610 as an example. The apparatus may further include: an input device 630 and an output device 640.
The processor 610, memory 620, input devices 630, and output devices 640 may be connected by a bus or other means, for example in fig. 3.
Memory 620, as a non-transitory computer readable storage medium, may be used to store non-transitory software programs, non-transitory computer executable programs, and modules. The processor 610 executes various functional applications of the electronic device and data processing, i.e., implements the processing methods of the method embodiments described above, by running non-transitory software programs, instructions, and modules stored in the memory 620.
Memory 620 may include a storage program area that may store an operating system, at least one application program required for functionality, and a storage data area; the storage data area may store data, etc. In addition, memory 620 may include high-speed random access memory, and may also include non-transitory memory, such as at least one magnetic disk storage device, flash memory device, or other non-transitory solid state storage device. In some embodiments, memory 620 optionally includes memory remotely located relative to processor 610, which may be connected to the processing device via a network. Examples of such networks include, but are not limited to, the internet, intranets, local area networks, mobile communication networks, and combinations thereof.
The input device 630 may receive input numeric or character information and generate signal inputs. The output device 640 may include a display device such as a display screen.
The one or more modules are stored in the memory 620 and, when executed by the one or more processors 610, perform: the invention relates to a reaction heat effect test analysis method of a slow chemical reaction process based on Raman spectrum. The product can execute the method provided by the embodiment of the invention, and has the corresponding functional modules and beneficial effects of the execution method. Technical details not described in detail in this embodiment may be found in the methods provided in the embodiments of the present invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (13)
1. The reaction thermal effect test analysis method based on Raman spectrum is characterized by comprising the following steps:
in the slow chemical reaction or low exothermic load chemical reaction process, synchronously performing a reaction calorimetric test and an in-situ Raman spectrum test;
generating a curve from the change data of the active functional groups read by the in-situ Raman spectrum test, wherein the curve is used as a calibration standard of a calorimetric curve; the step of generating a curve from the change data of the active functional groups read by the in-situ Raman spectrum test specifically comprises the following steps: normalizing the change data of the characteristic peak intensity of the active functional group, which is read by the in-situ Raman spectrum test, along with time to generate a Raman basic thermal analysis standard curve;
carrying out dynamic optimization matching on the heat accumulation curve obtained finally by the reaction calorimetric test relative to the change curve of the active functional group, thereby obtaining a reaction heat effect curve through integration; the dynamic optimization matching specifically comprises the following steps: two lever lines are arranged at the starting point of integration, and the heat release accumulation curve is obtained by adjusting the slope of the lever lines to be optimized, so that the heat release accumulation curve is consistent with the Raman basic thermal analysis standard curve.
2. The method for analyzing a thermal effect test of a reaction based on raman spectroscopy according to claim 1, further comprising, before the simultaneous testing: and measuring the spectrogram of each reactant in the slow chemical reaction process or the low exothermic load chemical reaction process, and marking the characteristic peak of the active functional group which possibly reacts.
3. The method for testing and analyzing the thermal effect of reaction based on the raman spectrum according to claim 1, wherein the thermal accumulation curve is obtained by the following steps: and converting the exothermic power curve obtained by the reaction calorimetric test into a heat accumulation curve.
4. The method of claim 1, wherein the reactive functional groups that may react during the slow chemical reaction include: a carbon-carbon double bond, a carbon-carbon triple bond, an azo bond, or a peroxy bond; the reactants in the slow chemical reaction process are organic matters or inorganic matters; the reaction system is an organic system, a water system or an oil-water mixed system.
5. The method for testing and analyzing the reaction thermal effect based on the Raman spectrum according to claim 1, wherein a Raman spectrometer is arranged outside a reaction kettle, the reaction kettle is a glass kettle, a quartz kettle or a reaction kettle made of metal, and a transparent window is arranged on the reaction kettle.
6. The method according to claim 1, wherein the progress of the reaction of the slow chemical reaction or the low exothermic load chemical reaction is monitored by the trend of the reactive functional group.
7. A method for analyzing a thermal effect test of a reaction based on raman spectroscopy according to claim 3, wherein the process of obtaining the thermal accumulation curve specifically comprises: and (3) giving a baseline initial value to the exothermic power curve obtained by the calorimetric test and integrating and converting the baseline initial value into the heat accumulation curve.
8. The method according to claim 7, wherein the integration method of the integration-to-thermal accumulation curve is a dynamic bezier method, a tangential method or a linear method.
9. A raman spectrum-based thermal effect testing and analyzing device for a thermal effect test of a slow chemical reaction process or a low exothermic load chemical reaction process, comprising:
the functional group change curve generating unit is used for generating a curve from the active functional group change data read by the in-situ Raman spectrum test and taking the curve as a calibration standard of the calorimetric curve; the functional group change curve generation unit further comprises a normalization processing subunit, which is used for normalizing the change data of the intensity of the characteristic peak of the active functional group, which is read by the in-situ Raman spectrum test, along with time;
the heat accumulation curve conversion unit is used for converting the exothermic power curve obtained by the reaction heat test into a heat accumulation curve;
the optimizing and matching unit is used for dynamically optimizing and matching the heat accumulation curve relative to the change curve of the active functional group so as to integrate and obtain a reaction heat effect curve; the optimization matching unit further comprises a slope adjustment subunit, wherein the slope adjustment subunit is used for setting two lever lines at an integration starting point, and the heat accumulation curve is obtained by adjusting the slope optimization of the lever lines.
10. The raman spectrum-based thermal reaction effect test analysis apparatus according to claim 9, further comprising: and a measuring and marking unit for measuring the spectrogram of each reactant in the slow chemical reaction process or the low exothermic load chemical reaction process and marking the characteristic peak of the active functional group possibly occurring in the reaction.
11. The raman spectrum-based reaction thermal effect test analysis apparatus according to claim 9, wherein the heat accumulation curve conversion unit further comprises an integration subunit for giving a baseline initial value to the exothermic power curve obtained by the reaction calorimetric test and integrating.
12. A memory comprising a set of instructions adapted to cause a processor to perform the steps of the raman spectrum based thermal response testing analysis method according to any one of claims 1 to 8.
13. A raman spectrum-based reaction thermal effect test analysis apparatus comprising a bus, an input device, an output device, a processor and a memory as claimed in claim 12;
the bus is used for connecting the memory, the input device, the output device and the processor;
the input device and the output device are used for realizing interaction with a user;
the processor is configured to execute the set of instructions in the memory.
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