CN114199937B - Calorimetric test method for ultralow temperature reaction - Google Patents
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Abstract
The invention relates to a test method of reaction heat in an ultralow temperature reaction process, in particular to a test method and a test device of ultralow temperature reaction heat under the condition of constant temperature obtained by reducing a system to a low temperature required by a process through an external circulation ultralow temperature cooling system and then utilizing a heat compensation mode. The device comprises a reactor system, a liquid feeding system, a gas feeding system, a compensation heater system, a central control system and a data processing system, and can realize ultralow-temperature constant-temperature calorimetric test of semi-batch reaction, and the operating temperature can be as low as-150 ℃.
Description
Technical Field
The invention relates to reaction heat test in an ultralow temperature reaction process, in particular to a test method and a test device for acquiring ultralow temperature reaction heat under a constant temperature condition by utilizing a heat compensation heat measuring mode.
Background
The precise energy release condition in the chemical reaction process is obtained through testing, and the method has great significance for chemical design and safe production. At present, instruments and equipment capable of realizing reaction calorimetry in the market are mainly a full-automatic reaction calorimeter (RC 1/Simular), an acceleration calorimeter (ARC), a Differential Scanning Calorimeter (DSC) and the like, and due to the limitations of the equipment and the method, the service temperature range of the equipment mainly takes high temperature, and the low temperature region does not exceed minus 60 ℃, so that the purpose of carrying out calorimetry test on ultralow temperature reaction in chemical production cannot be realized. As in the typical literature "pitavastatin calcium related substance synthesis", the synthesis of the "related substance (3)" is carried out at-78 ℃, but the above-mentioned devices cannot carry out calorimetric tests on the reaction process; in the literature "research and characterization of synthesis process of 2, 4-difluorophenylboronic acid", 2, 4-difluorophenylboronic acid is also synthesized at-78 ℃, but the calorimetric test of the reaction process cannot be carried out by using the equipment.
Disclosure of Invention
The invention aims to provide a calorimetric test method and a device for obtaining ultralow temperature reaction under a constant temperature condition by using a thermal compensation calorimetric mode.
In order to achieve the purpose, the invention adopts the technical scheme that:
a calorimetric test method for ultralow temperature reaction is characterized by that after the chemical reaction raw material is added into the reactor, the stable compensation calorimetric is applied to the reactor, and the material is added at reaction temp. to maintain reaction temp. constant, and the consumption difference of compensation calorimetric is the reaction heat of said chemical reaction.
The chemical reaction temperature range is-150 to 300 ℃, and the pressure is 0 to 200bar.
The chemical reaction is a batch or semi-batch gas-liquid, liquid-liquid or solid-liquid reaction.
The method specifically comprises the following steps:
1) Filling a substrate, namely adding a reaction substrate (raw material, a solvent and a catalyst) into a reactor;
2) Cooling, namely cooling the reaction system to a low temperature of (-150 to 300 ℃) through an external circulation cooling device;
3) Correcting, namely starting a compensation heater to maintain the temperature at the reaction temperature to finish correction;
4) Feeding, wherein raw materials enter a reactor at a constant speed through metering control, and the reaction temperature and the jacket temperature are kept consistent with those in a calibration state all the time through compensating power change of a heater;
5) Data acquisition, namely controlling by a testing device to ensure that the reaction temperature and the jacket temperature are constant, controlling by the device that raw materials are added into a reactor at a constant speed, and acquiring the power value of a compensating heater and the pressure parameter in the reactor in real time;
6) And (3) acquiring data through the test according to the heat balance in the reactor, and calculating the total reaction heat (apparent reaction heat) to further obtain apparent molar reaction heat in the reaction process, namely calorimetric heat of the ultralow-temperature reaction.
And 6) acquiring data in the constant-temperature heat flow mode, testing the heat power acquired to represent the heat in unit time, wherein the heat balance existing in the reactor is as follows:
in the formula, Q r Is the energy release in the reaction process; q a Thermally compensating the introduced energy for the compensating heater; q b To remove heat; q c Heat loss to the reactor; q d Sensible heat of the raw materials introduced in the charging process is J;
calibration phase, no reaction heat release of the system and sensible heat introduced during charging, thus Q r And Q d Is 0, then equation (1) becomes:
therefore, the temperature of the molten metal is controlled,
in the formula, Q a0 To compensate for the energy of the heater thermal compensation, J;
when the reaction temperature T is r Temperature T of jacket j When stable, the power of the compensating heater is constant and is recorded as q 0 Thus, there are:
substituting (4) into (3) and then substituting into (1), then:
integrating the above equation, one can obtain:
in the formula, t 1 To start the dropping, t 2 To end the dropping time, t 3 After the dripping is finished, the thermal compensation power stabilizes again;
for sensible heat of feed, there are:
Q d ＝m i C p (T r -T dose )(t 2 -t 1 ) (7)
in the formula, m i Mass flow rate for charging, g/s; c p The specific heat capacity of the additive is J DEG C -1 ·g -1 ；T r The reaction temperature, DEG C; t is dose The temperature of the feed is measured at DEG C;
substituting (7) into (6), then:
when the mass of a certain reactant A in the reactor is m and the molecular weight is Mr, the apparent molar reaction heat metered by the substance A is as follows:
in the formula, delta H m Is apparent molar reaction heat (based on the moles of the reactant A) (unit is J.mol) -1 )。
A device special for the method comprises a sample feeding system, an ultralow temperature circulating cooling system, a reactor system, a compensating heater system 51 and a central control system, wherein the sample feeding system comprises a liquid feeding system and a gas feeding system, the liquid feeding system and the gas feeding system are respectively connected with the reactor system, the ultralow temperature circulating cooling system is arranged outside the reactor system, the compensating heater system is inserted into a reactor of the reactor system and is in direct contact with materials, and real-time reaction parameters of the reactor system are detected through the central control system.
The liquid feeding system comprises a liquid raw material bottle 11, a spherical valve 12, a check valve 13, a precision liquid feeding pump 14 and a check valve 15, wherein the liquid raw material bottle 11, the spherical valve 12, the check valve 13, the precision liquid feeding pump 14 and the check valve 15 are sequentially connected in series through a pipeline 16 and are connected into the sample reactor; the gas feeding system comprises a gas raw material steel cylinder 21, a pressure control system 22, a needle valve 23, a check valve 24, a precision gas mass flowmeter 25 and a check valve 26, wherein the gas raw material steel cylinder 21, the pressure control system 22, the ball valve 23, the check valve 24, the precision gas mass flowmeter 25 and the check valve 26 are sequentially connected through a pipeline 27 and are connected into the sample reactor.
The ultralow temperature circulating cooling system comprises a cooling medium outlet temperature sensor 31, a check valve 32, a circulating temperature controller 34, a liquid circulating pump 35, a check valve 36, a cooling medium inlet temperature sensor 37 and a heat-insulating jacket 38, wherein a cooling medium is filled in the jacket and is discharged from the left lower end of the jacket and the right upper end of the jacket, and then enters the circulating pump for circulating again, the temperature sensors are arranged at the inlet and outlet ends of the jacket and are responsible for collecting data and feeding back the data to the circulating temperature controller, and the circulating temperature controller performs heating and cooling operations through a PID control system to ensure the constant temperature of the ultralow temperature cooling medium entering the jacket. The cooling medium outlet temperature sensor 31, the check valve 32, the circulation temperature controller 34, the liquid circulation pump 35, the check valve 36, the cooling medium inlet temperature sensor 37, and the heat retention jacket 38 are connected in series in this order via the pipe 33.
The reactor system comprises a sample reactor 41, a reaction furnace 42 (provided with a heating system), a ball valve 43, an electromagnetic valve 44 and a magnetic stirring 45. The sample reactor is provided with a temperature sensor, a pressure sensor and a voltage signal sensor and is connected with a central control system.
The invention has the advantages that:
1. the device is provided with the ultralow temperature cooling circulation system, can reduce the reaction temperature to-150 ℃, can perform calorimetric reaction on various ultralow temperature reactions, can perform constant-temperature intermittent and semi-intermittent reaction calorimetric reaction, and solves the problem of difficult calorimetric reaction at ultralow temperature.
2. The device accurately controls the compensation power through the PID control system, can ensure that the reaction temperature and the jacket temperature are kept constant in the reaction process, and can acquire the thermal compensation power value in real time through the prepared signal acquisition system.
3. The device can implement precise control on the ultralow temperature reaction process under the constant temperature condition, and realize real-time online acquisition and analysis of data. The reactor system is provided with a sample reactor, and a PT100 temperature sensor which is three-dimensional and symmetrical at multiple points is arranged around the sample reactor, so that the reaction temperature can be accurately controlled, and the accurate heat change condition in the reaction process can be obtained. PT100 temperature sensors are arranged at the cooling medium inlet and the cooling medium outlet of the ultralow temperature cooling circulation system, so that the temperature of the jacket can be accurately controlled. The input end of the sample reactor is provided with a pressure sensor for detecting the pressure of the reactor in real time, and the gas flow rate and the reaction pressure can be accurately controlled through a PID control system. The input end of the sample reactor is connected with a precise liquid feeding pump, and the precise control of the liquid flow rate can be realized through a PID control system.
The central control system of the device is a single chip microcomputer, a PLC, an intelligent instrument and a central control system which are embedded with switch control, proportional action, integral action, differential action and even PID algorithm, can convert and display the acquired signals and output control signals according to feedback signals, can acquire, process and display the power, temperature and pressure signals of the thermal compensation heater, and can adjust the behaviors of the power control unit, the temperature control unit and the pressure control unit of the thermal compensation heater in real time according to the feedback signals.
4. The device can test the reaction heat at ultralow temperature, and can play a more practical and effective guiding role in realizing the engineering design related to energy conversion and transfer, process safety and process optimization.
5. The reaction heat test in the ultralow temperature reaction process is carried out by utilizing the thermal compensation power, and the compensation heater is directly contacted with the material, so that the thermal compensation power loss can be reduced to the greatest extent, and the accurate reaction heat can be obtained; meanwhile, the measuring method of the invention can also be suitable for measuring reaction heat of various calorimetric devices.
Drawings
FIG. 1 is a schematic structural view of an apparatus according to an embodiment of the present invention, in which 11 is a liquid material bottle, 12 is a first ball valve, 13 is a first check valve, 14 is a precision liquid feed pump, 15 is a second check valve, and 16 is a first pipeline; 21 is a gas cylinder, 22 is a first pressure control system, 23 is a first needle valve, 24 is a third check valve, 25 is a gas mass flow meter, 26 is a fourth check valve, and 27 is a second pipeline. All the above are reactor feed systems.
31 is a first outlet temperature sensor of ultra-low temperature cooling medium, 32 is a fifth check valve, 33 is a third pipeline, 34 is a circulating temperature controller, 35 is a cooling medium circulating pump, 36 is a sixth check valve, 37 is a second inlet temperature sensor of cooling medium, and 38 is a heat preservation jacket. All the above steps are ultra-low temperature cooling circulation systems.
41 is a reaction tank; 42 is a reaction furnace which is provided with a heating system; 43 is a second ball valve; solenoid valve 44 and magnetic stirring 46.
And 51 a thermally compensated heater system.
FIG. 2 is a graph of time-temperature-thermal compensation power of a reaction process of reacting diketene with chlorine to generate an intermediate 4-chloro-3-oxobutanoyl chloride provided in example 2 of the present invention.
FIG. 3 is a graph of time-temperature thermal compensation power of a reaction process in which 2-bromonaphthalene reacts with n-butyllithium to generate an intermediate 2-lithium naphthalene according to example 3 of the present invention.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Example 1
As shown in fig. 1, the apparatus comprises a sample feeding system, an ultra-low temperature circulating cooling system, a reactor system and a central control system, wherein the sample feeding system comprises a liquid feeding system and a gas feeding system, wherein the liquid feeding system comprises a liquid raw material bottle 11, a ball valve 12, a check valve 13, a precision liquid feeding pump 14 and a check valve 15, the liquid raw material bottle 11, the ball valve 12, the check valve 13, the precision liquid feeding pump 14 and the check valve 15 are connected in series in sequence through a pipeline 16 and are connected into a sample reactor; the gas feeding system comprises a gas raw material steel cylinder 21, a pressure control system 22, a needle valve 23, a check valve 24, a precision gas mass flowmeter 25 and a check valve 26, wherein the gas raw material steel cylinder 21, the pressure control system 22, the ball valve 23, the check valve 24, the precision gas mass flowmeter 25 and the check valve 26 are sequentially connected through a pipeline 27 and are connected into the sample reactor.
Ultralow temperature circulative cooling system includes coolant outlet temperature sensor 31, check valve 32, circulation temperature controller 34, liquid circulating pump 35, check valve 36, coolant inlet temperature sensor 37 and heat preservation jacket 38, there is coolant in the jacket, let in from the lower left end of jacket, and discharge from the upper right end, then get into the circulating pump mesocycle once more, the jacket exit end all is equipped with temperature sensor, be responsible for the data acquisition feedback to circulation temperature controller, circulation temperature controller passes through PID control system, rise, the operation of cooling, guarantee to get into the ultralow temperature coolant temperature constancy in the jacket. The cooling medium outlet temperature sensor 31, the check valve 32, the circulation temperature controller 34, the liquid circulation pump 35, the check valve 36, the cooling medium inlet temperature sensor 37, and the heat retention jacket 38 are connected in series in this order via the pipe 33.
The reactor system comprises a sample reactor 41, a reaction furnace 42 (provided with a heating system), a ball valve 43, an electromagnetic valve 44 and a magnetic stirring 45. The sample reactor is provided with a temperature sensor, a pressure sensor and a voltage signal sensor and is connected with a central control system.
And the compensating heater system 51 changes the thermal compensation power in real time according to the heat release condition of the system, keeps the reaction temperature and the jacket temperature constant, acquires power signals in real time, and is connected with a central control system.
In this embodiment, the central control system is a PID control system, and a single chip microcomputer with various on-off controls and PID algorithms is embedded in the central control system, so that signal conversion and display can be performed on the acquired signals, control signal output can be performed according to the feedback signals, acquisition, processing and display of temperature and pressure signals can be realized, and the temperature and the pressure can be adjusted in real time according to the feedback signals. The central control system is well known in the art.
Example 2
In this embodiment, the calorimetric test method of the present invention is illustrated by taking the example of the reaction of diketene and chlorine to generate the intermediate 4-chloro-3-oxobutanoyl chloride, and further verified by bond energy calculation.
The test steps are as follows:
1) Filling a substrate, and adding 0.5003g of diketene and 2.003g of dichloromethane into a reactor;
2) Cooling, cooling by external circulation cooling device to clamp the sleeve T j Cooling to-80 deg.C;
3) Correcting, starting the compensating heater to make the reaction temperature T r Maintaining at-70 deg.C, waiting for reaction at temperature T r After stabilizing at-70 ℃, finishing correction; measurement gives q 0 ＝485mW；
4) Feeding, introducing chlorine (T) into the reactor dose =25 ℃), the sample mass flow meter was controlled to 6.7 × 10 -5 Introducing chlorine into the sample reactor at a flow rate of g/s, and reacting diketene in the reactor with the chlorine to generate a product 4-chloro-3-oxobutyryl chloride;
5) Data acquisition, namely controlling by a testing device to ensure that the reaction temperature and the jacket temperature are constant, controlling by the device that raw materials are added into a reactor at a constant speed, acquiring the power value of a compensating heater in real time, recording the experimental phenomenon until the experiment is finished, and calculating to obtain apparent reaction heat;
6) Moment of onset of ventilation t 1 =56.0min = -3360s, and ventilation time t is ended 2 =116.0min = 69660 s, and after the ventilation is finished, the thermal compensation power stabilizes the time t again 3 ＝170.0min＝10200s；q 0 ＝485mW；m i ＝6.7×10 -5 g/s; specific heat capacity of chlorine gas C p ＝0.476J·℃ -1 ·g -1 (ii) a The feeding amount of the diketene is m =0.5003g; m =84.07g · mol -1 ；
7) All the values are substituted into the formula (9), and the apparent heat of reaction of the diketene chlorination is-213.0 kJ.mol through integral calculation -1 (based on moles of diketene).
8) And (5) verifying the result. Consult through literature: O-C bond energy-326 kJ/mol, C = C bond energy-611 kJ/mol, cl-Cl bond energy 243kJ/mol, C = O bond energy-728 kJ/mol, C-Cl bond energy-328 kJ/mol, C-C bond energy-332 kJ/mol, bond energy calculation result:
Δ r h = (-728-2X 328-332) - (-326X 2-611-243) = -210kJ/mol (based on the molar number of the diketene), and the error of the reaction heat obtained by the method and the value reported by the literature is 1.4 percent and is not more than 5 percent.
Therefore, the method can be used for testing the reaction heat in the low-temperature reaction process, and has the advantages of small error and accurate and credible data.
Example 3
In this embodiment, the calorimetric test method of the present invention is illustrated by taking the example of the reaction of 2-bromonaphthalene with n-butyllithium to produce an intermediate 2-lithium naphthalene.
The test steps are as follows:
1) Filling a substrate, and adding 1.5000g of 2-bromonaphthalene and 4.000g of tetrahydrofuran into a reactor;
2) Cooling, replacing with nitrogen, and cooling jacket T by external circulation cooling device j Cooling to-90 deg.C;
3) Correcting, starting the compensating heater to make the reaction temperature T r Maintained at-78 deg.C, reaction temperature T r After stabilization at-78 deg.C, the calibration is terminated and q is determined 0 ＝300mW；
4) Feeding, dropwise adding 2.5mol/L n-butyllithium n-hexane solution (T) into the reactor dose 2.496g at the temperature of 25 ℃, controlling a sample mass flowmeter to drop into a sample reactor at the flow rate of 4.6 multiplied by 10 < -4 > g/s, and reacting n-butyl lithium in the reactor with 2-bromonaphthalene to generate a product 2-lithium naphthalene;
5) Data acquisition, namely controlling by a testing device to ensure that the reaction temperature and the jacket temperature are constant, controlling by the device that raw materials are added into a reactor at a constant speed, acquiring the power value of a compensating heater in real time, recording the experimental phenomenon until the experiment is finished, and calculating to obtain apparent reaction heat;
6) Moment t of starting charging 1 =60.0min =3600s, and end of charging time t 2 =150.0min =9000s, and after the dripping is finished, the thermal compensation power stabilizes the time t again 3 ＝220.0min＝13200s；mi＝4.6×10 -4 g/s; specific heat capacity C of n-butyllithium solution p ＝2.25J·℃ -1 ·g -1 (ii) a The feeding amount of the 2-bromonaphthalene is m =1.5000g; m =207.07 g. ·mol -1 ；
7) Substituting all the numerical values into the formula (9), and obtaining the 2-lithium naphthalene intermediate with the synthetic apparent reaction heat of-129.9 kJ.mol through integral calculation -1 (based on the mole number of 2-bromonaphthalene).
In conclusion, the invention adopts a specific device to obtain the difference value between the thermal compensation power and the initial correction power in the reaction process, further calculates and obtains the heat, and is suitable for the measurement of ultralow-temperature intermittent or semi-intermittent gas-liquid, liquid-liquid or solid-liquid reaction heat due to simple operation, accurate measured data and accurate temperature control.
Claims (3)
1. A calorimetric test method of ultralow temperature reaction is characterized in that: after chemical reaction raw materials are added into a reactor, applying stable compensation heat to the reactor, adding materials at a reaction temperature, maintaining the reaction temperature constant, and obtaining the reaction heat of the chemical reaction along with the consumption difference of the compensation heat in the reaction process;
the method specifically comprises the following steps:
1) Filling a substrate, and adding a reaction substrate into a reactor;
2) Cooling, namely reducing the reaction system to the reaction temperature through an external circulation cooling device;
3) Correcting, namely starting a compensation heater to maintain the temperature at the reaction temperature to finish correction;
4) Feeding, wherein raw materials enter a reactor at a constant speed through metering control, and the reaction temperature and the jacket temperature are kept consistent with those in a calibration state all the time through compensating power change of a heater;
5) Data acquisition, namely controlling by a testing device to ensure that the reaction temperature and the jacket temperature are constant, controlling by the device that raw materials are added into the reactor at a constant speed, and acquiring the power value of a compensating heater and the pressure parameter in the reactor in real time;
6) According to the heat balance in the reactor, data are obtained through the test, the total reaction heat is calculated, and further the apparent molar reaction heat in the reaction process is obtained, so that the calorimetric quantity of the ultralow temperature reaction is obtained;
and 6) acquiring data in the constant-temperature heat flow mode, testing the heat power acquired to represent the heat in unit time, wherein the heat balance in the reactor is as follows:
in the formula, Q r Is the energy release in the reaction process; q a Thermally compensating the introduced energy for the compensating heater; q b To remove heat; q c Heat loss to the reactor; q d Sensible heat of the raw materials introduced in the charging process is J; calibration phase, no reaction heat release of the system and sensible heat introduced during charging, thus Q r And Q d Is 0, then equation (1) becomes:
therefore, the temperature of the molten metal is controlled,
in the formula, Q a0 To compensate for the energy of the heater thermal compensation, J;
when the reaction temperature T is r Temperature T of jacket j When stable, the power of the compensating heater is a constant value, recorded as q 0 Thus, there are:
substituting (4) into (3) and then substituting into (1), then:
integrating the above equation, one can obtain:
in the formula, t 1 To start the dropping, t 2 To end the dropping time, t 3 After the dripping is finished, the thermal compensation power stabilizes again;
for sensible heat of feed, there are:
Q d ＝m i C p (T r -T dose )(t 2 -t 1 ) (7)
in the formula, m i Is the mass flow of the feed in g/s; c p Specific heat capacity of the additive, J.DEG C -1 ·g -1 ；T r The reaction temperature, DEG C; t is dose The temperature of the material is measured at DEG C;
substituting (7) into (6), then:
when the mass of a certain reactant A in the reactor is m and the molecular weight is Mr, the apparent molar reaction heat metered by the substance A is as follows:
in the formula, delta H m Apparent molar heat of reaction in terms of moles of reactant A, in J.mol -1 ；
The external circulation cooling device is arranged outside the reactor;
the external circulation cooling device comprises a jacket;
the compensating heater is inserted into the reactor, is in direct contact with the material, and detects the real-time reaction parameters of the reactor through central control.
2. The calorimetry method for ultralow temperature reaction according to claim 1, wherein: the chemical reaction temperature range is-150 to 300 ℃, and the pressure is 0 to 200bar.
3. The calorimetry method for ultralow temperature reaction according to claim 1, wherein: the chemical reaction is a batch or semi-batch gas-liquid, liquid-liquid or solid-liquid reaction.
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