Method and device for testing continuous flow reaction heat by using reference calorimetry
Technical Field
The invention relates to a method and a device for testing reaction heat in a continuous flow reaction process, in particular to a method and a device for testing the reaction heat of a continuous flow by using reference calorimetry.
Background
The apparent reaction heat is the comprehensive expression of energy released or absorbed in the chemical reaction process and is an important parameter required by chemical design and safe production. At present, reaction calorimetric test instruments for realizing industrial production in the market mainly comprise a reaction calorimeter (RC1/Simular), an acceleration calorimeter (ARC), a Differential Scanning Calorimeter (DSC) and the like, all the equipment are laboratory scale devices, and mainly aim at reaction heat tests of kettle type intermittent and semi-intermittent processes, such as a typical document 'thermal safety research of ethyl butyrate synthesis process' that RC1 is adopted to carry out calorimetric test on ethyl butyrate synthesis, n-butanol is used as a bottoming material in the test process, acetic anhydride is dripped to complete the calorimetric test, and the reaction is a liquid-liquid homogeneous reaction; the research on the heat release characteristic of the alcoholysis process of the acetic anhydride is obtained by adopting RC1 and ARC to carry out the thermal characteristic of the alcoholysis reaction of the acetic anhydride, the reaction is also a liquid-liquid homogeneous reaction, the test process of RC1 is to add methanol into the acetic anhydride to finish the calorimetric test, the test process of ARC is to keep the methanol and the acetic anhydride at low temperature, and the test pool is quickly arranged in a test system to finish the calorimetric test; however, none of the above mentioned reaction calorimetric testers can achieve continuous flow process reaction heat test with continuous discharge and continuous feeding.
Disclosure of Invention
The invention aims to provide a method and a device for testing continuous flow reaction heat by using reference calorimetry
In order to achieve the purpose, the invention adopts the technical scheme that:
a continuous flow reaction thermal device for testing by using reference heat comprises a reference feeding and discharging system A, a sample feeding and discharging system B, a reactor system and a central control system, wherein the reactor system is provided with a sample reactor and a reference reactor, the reference feeding and discharging system A comprises a liquid raw material bottle A, a gas raw material bottle A, a mixer A, a sampler A and a gas-liquid separator A, wherein the liquid raw material bottle A and the gas raw material bottle A are respectively connected with the mixer A, the reference reactor, the sampler A and the gas-liquid separator A are sequentially connected in series, the sample feeding and discharging system B comprises a liquid raw material bottle B, a gas raw material bottle B, a mixer B, a sampler B and a gas-liquid separator B, the mixer B, the sample reactor, the sampler B and the gas-liquid separator B are connected in series in sequence; all be equipped with accurate liquid charge pump between liquid raw material bottle A and the blender A and between liquid raw material bottle B and the blender B, all be equipped with gas flowmeter between gaseous raw material bottle A and the blender A and between gaseous raw material bottle B and the blender B, all be equipped with the solenoid valve between reference reactor and the sampler A and between sample reactor and the sampler B, all be equipped with pressure sensor, temperature sensor and voltage signal sensor on sample reactor and the reference reactor, accurate liquid charge pump, gas flowmeter, solenoid valve, pressure sensor, temperature sensor and voltage signal sensor all link to each other with central control system.
A first ball valve A, a first one-way valve A, a precise liquid feeding pump A and a second one-way valve A are sequentially arranged on a first pipeline A between the liquid raw material bottle A and the mixer A along the transmission direction.
And a first pressure gauge A, a needle valve A, a second ball valve A, a third one-way valve A, a gas flowmeter A and a fourth one-way valve A are sequentially arranged on a second pipeline A between the gas raw material bottle A and the mixer A along the transmission direction.
And a check valve A is arranged on a third pipeline A between the mixer A and the reference reactor.
And an electromagnetic valve A and a second pressure gauge A are sequentially arranged on a fourth pipeline A between the reference reactor and the sampler A along the transmission direction.
And a first ball valve B, a first one-way valve B, a precise liquid feeding pump B and a second one-way valve B are sequentially arranged on a first pipeline B between the liquid raw material bottle B and the mixer B along the transmission direction.
And a first pressure gauge B, a needle valve B, a second ball valve B, a third check valve B, a gas flowmeter B and a fourth check valve B are sequentially arranged on a second pipeline B between the gas raw material bottle B and the mixer B along the transmission direction.
And a check valve B is arranged on a third pipeline B between the mixer B and the sample reactor.
And an electromagnetic valve B and a second pressure gauge B are sequentially arranged on a fourth pipeline B between the sample reactor and the sampler B along the transmission direction.
A method for testing heat of continuous flow reaction by using reference calorimetric method includes continuously adding raw materials into sample reactor and reference reactor at the same flow rate, controlling reaction residence time by feeding speed and system pressure, collecting voltage signal deviation baseline value △ U of system voltage signal in reaction process in real time by using reference calorimetric method and constant temperature mode or scanning mode, calculating reaction heat release rate Q (unit is mW) and heat absorption and release quantity Q in reaction process when heat flow of reaction system is stable according to deviation baseline value △ U (unit is muV) of real-time voltage signalr(unit is J) and then the apparent heat of reaction △ H is obtained by calculating the heat absorption and release quantity in the reaction processm。
In a further aspect of the present invention,
1) calibration, namely transmitting pulse signals with fixed time at fixed intervals according to the length and the interval of the pulse, performing a cycle test in a target temperature range, and obtaining sensitivity (formula (1)) through joule effect (pulse signals);
in the formula, aiFor different cyclic sensitivities (in units of muV mW) at different temperatures-1) I is the number of cycles, QiTo integrate the voltage peak area obtained for each pulse (in μ V · s), T is the temperature (in K), P is the power (in mW), and T is the timeM (in s);
fitting the sensitivity of the reciprocating circulation at different temperatures to obtain the temperature T and the sensitivity aiAnd (2) and obtaining a multistage sensitivity coefficient bnN is a natural number starting from 0;
ai(T)=b0+b1T+b2T2+b3T3+b4T4+…… (2)
wherein T is temperature (in K);
2) charging, charging solid or liquid reaction raw materials into a sample reactor, fixing the sample reactor at an outlet of the reactor, designing the bed thickness of materials such as a catalyst and the like according to process requirements, heating up or heating up to a target temperature at a constant rate, and waiting for a system voltage signal baseline to be stable.
3) Feeding, continuously adding raw materials into the sample and reference reactor, controlling the flow rates of the materials at two sides to be completely consistent, controlling the reaction residence time by the feeding speed and the system pressure, and acquiring △ U of the deviation of the system voltage signal from the baseline value in the reaction process in real time on line
4) When the reaction system is stable, stopping feeding the sample and the reference reactor, wherein the feeding time is t0Obtaining the feed mass W (in g), t0The voltage signal is integrated over a period of time from the baseline value (equation (3)), and the peak area S is:
wherein S is the integrated peak area (in. mu.V.s), and P is the power (in mW)
Calculating the heat absorption and release quantity Q of the reaction process according to the sensitivity a (T) of different temperaturest0(formula (4))
In the formula, Qt0For the heat absorption and release (unit is J)
The conversion relationship between the mole number of the reactant and the mass of the reactant is as follows:
m0is t0The number of moles (in moles) of a certain reactant added over a period of time; w is t0A certain amount of reactant mass (in g) added over a period of time; m is the molar mass (in g. mol) of a certain reactant added-1)
Apparent molar heat of reaction △ H in the course of the reactionmComprises the following steps:
in the formula, △ HmApparent molar heat of reaction (in moles of a certain reactant) (in kJ. mol.)-1)。
The reaction temperature range is from room temperature to 600 ℃, the pressure is 0-400bar, and the heating rate is 0-2 K.min-1The flow rate of the sample gas is 0.05-1000 mL/min-1The flow rate of the sample injection liquid is 0.001-200 mL/min-1。
In a still further aspect of the present invention,
1) calibration, in order to obtain an accurate heat flow value, a sensitivity test is required, and the sensitivity changes along with the change of temperature.
Before the test, the length and the interval of the pulse are set according to the specification range of the instrument, a series of pulse signals with fixed time are transmitted at fixed intervals, and the cyclic test is carried out in a target temperature range.
The voltage peak area obtained for each pulse is taken at a given power P (in mW) over time t and waiting for the return of the magnitude voltage signal at the initial baseline, resulting in an integral value Qi(unit is. mu.V.s) and adding Qi(in μ V · s) divided by the product of the power P (in mW) and the time t (in s), which defines the amount of heat given by the joule effect, represents the sensitivity coefficient a (in μ V · mW)-1) Namely:
in the formula, aiFor different cyclic sensitivities (in units of muV mW) at different temperatures-1) I is the number of cycles, QiTo integrate the area of the voltage peaks obtained for each pulse (in μ V · s), T is the temperature (in K), P is the power (in mW), T is the time (in s)
Fitting the sensitivity of the reciprocating circulation at different temperatures to obtain the temperature T and the sensitivity aiAnd (2) and obtaining a multistage sensitivity coefficient bnAnd n is a natural number starting from 0.
ai(T)=b0+b1T+b2T2+b3T3+b4T4+…… (2)
Wherein T is temperature (in K);
2) charging, charging solid or liquid reaction raw materials into a sample reactor, fixing the sample reactor at an outlet of the reactor, designing the bed thickness of materials such as a catalyst and the like according to process requirements, heating up or heating up to a target temperature at a constant rate, and waiting for a system voltage signal baseline to be stable.
3) Feeding, continuously adding raw materials into the sample and reference reactor, controlling the flow rates of the materials at two sides to be completely consistent, controlling the reaction residence time by the feeding speed and the system pressure, and acquiring △ U of the deviation of the system voltage signal from the baseline value in the reaction process in real time on line
4) When the reaction system is stable, stopping feeding the sample and the reference reactor, wherein the feeding time is t0Obtaining the feed mass W (in g), t0The voltage signal is integrated over a time period away from the baseline value (equation (2)), and the peak area S is:
wherein S is the integrated peak area (in. mu.V.s), and P is the power (in mW)
Calculating the heat absorption and release quantity Q of the reaction process according to the sensitivity a (T) of different temperaturest0(formula (4))
In the formula, Qt0For the heat absorption and release (unit is J)
The conversion relationship between the mole number of the reactant and the mass of the reactant is as follows:
m0is t0The number of moles (in moles) of a certain reactant added over a period of time; w is t0A certain amount of reactant mass (in g) added over a period of time; m is the molar mass (in g. mol) of a certain reactant added-1)
Apparent molar heat of reaction △ H in the course of the reactionmComprises the following steps:
in the formula, △ HmApparent molar heat of reaction (in moles of a certain reactant) (in kJ. mol.)-1)。
The reaction is a calorimetric test of gas-solid, gas-liquid and liquid-liquid phase continuous reactions.
The invention has the advantages that:
1. the device is simultaneously provided with the reference and sample reactors, liquid or gas is simultaneously fed into the reference and sample reactors in the reaction process, the flow velocity at two sides can be strictly controlled, the influence of material feeding sensible heat and vaporization latent heat can be directly deducted while the reaction is finished, vaporization heat absorption or feeding sensible heat is avoided to cover an exothermic signal, and the real heat change condition of the reaction is obtained.
2. The device can implement precise control on the gas-solid, gas-liquid and liquid-liquid continuous flow reaction process according to a constant temperature and scanning temperature rise mode, and can acquire and analyze data on line in real time. The reactor system is provided with a sample and reference test pool, and the PT100 temperature sensors which are three-dimensional and multi-symmetrical are arranged around the sample and reference pool, so that more accurate exothermic heat change condition can be obtained, and the temperature of the reaction furnace can be accurately controlled. The input end of the sample and reference reactor is provided with a pressure sensor for detecting the pressure of the reactor in real time, the gas feeding pipelines are connected with a pressure valve and a gas mass flowmeter, the output ends are provided with electromagnetic valves, and the gas flow rate, the reaction pressure and the residence time of reaction materials can be accurately controlled by a PID control system. In addition, the input ends of the sample and reference reactors are connected with a precise liquid feeding pump, and the flow rate, the reaction pressure and the reaction retention time of the liquid can be precisely controlled 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 temperature and pressure signals, and can adjust the behaviors of the temperature control unit and the pressure control unit in real time according to the feedback signals.
3. The device of the invention is adopted to measure the reaction heat of the gas-solid and gas-liquid continuous flow reaction process and the data of heat release rate, heat absorption rate and the like in the continuous flow reaction process in a constant temperature heat flow or scanning mode, and the heat release and heat absorption continuous flow reaction calorimetric test can be realized according to the reaction process conditions of the continuous flow through the control calculation of the control system.
4. The apparent result obtained by the continuous flow reaction calorimetric experiment test method can play a more practical and effective guiding role in realizing the engineering design related to energy conversion and transmission, process safety and process optimization.
Drawings
Figure 1 is a schematic structural diagram provided by an embodiment of the present invention,
FIG. 2 is a graph of sensitivity curves fitted to different temperatures according to an embodiment of the present invention.
Fig. 3 is a schematic diagram of voltage variation in the reaction process according to the embodiment of the present invention.
Wherein, a is a reference test system, 11 is a liquid raw material bottle a, 12 is a first ball valve a, 13 is a first check valve a, 14 is a precision liquid feeding pump a, 15 is a second check valve a, 16 is a gas raw material bottle a, 17 is a first pressure gauge a, 18 is a needle valve a, 19 is a second ball valve a, 110 is a third check valve a, 111 is a gas flowmeter a, 112 is a fourth check valve a, 113 is a mixer a, 114 is a check valve a, 115 is an electromagnetic valve a, 116 is a three-way valve a, 117 is a gas-liquid separator a, 118 is a sampler a, 119 is a second pressure gauge a, 120 is a first pipeline a, 121 is a second pipeline a, 122 is a third pipeline a, 123 is a fourth pipeline a;
b is a reference test system, 21 is a liquid raw material bottle B,22 is a first ball valve B, 23 is a first check valve B, 24 is a precision liquid feed pump B, 25 is a second check valve B, 26 is a gas raw material bottle B, 27 is a first pressure gauge B, 28 is a needle valve B, 29 is a second ball valve B, 210 is a third check valve B, 211 is a gas flow meter B, 212 is a fourth check valve B, 213 is a mixer B, 214 is a check valve B, 215 is an electromagnetic valve B, 216 is a three-way valve B, 217 is a gas-liquid separator B, 218 is a sampler B, 219 is a second pressure gauge B, 220 is a first pipeline B, 221 is a second pipeline B, 222 is a third pipeline B, 223 is a fourth pipeline B, and 224 is an online analyzer;
31 is a reaction furnace, 32 is a sample reactor, and 33 is a reference reactor.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
The method and the device can realize reaction heat test of gas-solid, gas-liquid, liquid-liquid and other continuous processes by utilizing a reference calorimetric principle, add reference substances with similar quality to reaction materials, eliminate the thermodynamic effect of the reactor in the reaction process, and can meet the reaction heat test requirements under different working conditions by adding a solid or liquid fixing device and a flow control and pressure control system to obtain more accurate reaction heat data.
Example 1
As shown in fig. 1, the method includes a reference feeding and discharging system a, a sample feeding and discharging system B, a reactor system and a central control system, wherein the reactor system includes a reaction furnace 31, a sample reactor 32 and a reference reactor 33, the sample reactor 32 and the reference reactor 33 are both disposed in the reaction furnace 31, the reference feeding and discharging system a and the sample feeding and discharging system B are two sets of parallel systems, wherein the reference feeding and discharging system a includes a liquid raw material bottle a11, a gas raw material bottle a16, a mixer a113, a sampler a118 and a gas-liquid separator a117, the liquid raw material bottle a11 and the gas raw material bottle a16 are respectively connected with the mixer a113 through pipelines, the mixer a113, the reference reactor 33, the sampler a118 and the gas-liquid separator a117 are sequentially connected in series, the sample feeding and discharging system B includes a liquid raw material bottle B21, a gas raw material bottle B26, a mixer B213, a sampler B218 and a gas-liquid separator B217, the liquid raw material bottle B21 and the gas raw material bottle B26 are respectively connected with a mixer B213 through pipelines, and the mixer B213, the sample reactor 32, the sampler B218 and the gas-liquid separator B217 are sequentially connected in series; the pipeline between the liquid raw material bottle A11 and the mixer A113 and the pipeline between the liquid raw material bottle B21 and the mixer B213 are respectively provided with a precision liquid feeding pump, the pipeline between the gas raw material bottle A16 and the mixer A113 and the pipeline between the gas raw material bottle B26 and the mixer B213 are respectively provided with a gas flowmeter, the pipeline between the reference reactor 33 and the sampler A118 and the pipeline between the sample reactor 32 and the sampler B218 are respectively provided with an electromagnetic valve, the sample reactor 32 and the reference reactor 33 are respectively provided with a pressure sensor, a temperature sensor and a voltage signal sensor, and the precision liquid feeding pump, the gas flowmeter, the electromagnetic valves, the pressure sensor, the temperature sensor and the voltage signal sensor are all connected with a central control system. The mixer, the reactor, the sampler, the gas-liquid separator and the reaction furnace 31 are all known in the art and are commercially available products, wherein a heating system is arranged in the reaction furnace 31.
As shown in fig. 1, a first ball valve a12, a first check valve a13, a precision liquid feeding pump a14 and a second check valve a15 are sequentially arranged on a first pipeline a120 between a liquid raw material bottle a11 and a mixer a113 along a transmission direction, a first pressure gauge a17, a needle valve a18, a second ball valve a19, a third check valve a110, a gas flow meter a111 and a fourth check valve a112 are sequentially arranged on a second pipeline a121 between a gas raw material bottle a16 and the mixer a113 along the transmission direction, a check valve a114 is arranged on a third pipeline a122 between the mixer a113 and a reference reactor 33, an electromagnetic valve a115 and a second pressure gauge a119 are sequentially arranged on a fourth pipeline a123 between the reference reactor 33 and a sampler a118 along the transmission direction, a three-way valve a116 is arranged on a pipeline between the sampler a118 and a gas-liquid separator a117, and the three-way valve a116 is connected to an online analyzer 224 through a line.
As shown in fig. 1, a first ball valve B22, a first check valve B23, a precision liquid feeding pump B24 and a second check valve B25 are sequentially arranged on a first pipeline B220 between a liquid raw material bottle B21 and a mixer B213 along a transmission direction, a first pressure gauge B27, a needle valve B28, a second ball valve B29, a third check valve B210, a gas flow meter B211 and a fourth check valve B212 are sequentially arranged on a second pipeline B221 between a gas raw material bottle B26 and the mixer B213 along the transmission direction, a check valve B214 is arranged on a third pipeline B222 between the mixer B213 and the sample reactor 32, an electromagnetic valve B215 and a second pressure gauge B219 are sequentially arranged on a fourth pipeline B223 between the sample reactor 32 and the sampler B218 along the transmission direction, a three-way valve B216 is arranged on a pipeline between the sampler B218 and the gas-liquid separator 217, and the three-way valve B216 is connected with an online analyzer 224 through a pipeline.
Check valves are arranged on input side and output side pipelines of the gas flowmeter A111 and input side and output side pipelines of the gas flowmeter B211, pressure reducing valves are arranged on pipelines between the liquid raw material bottle A11 and the first ball valve A12 and pipelines between the liquid raw material bottle B21 and the first ball valve B22, and feeding pressure sensors are arranged on input side and output side pipelines of the pressure reducing valves. The ball valve, the one-way valve, the precise liquid feeding pump, the pressure gauge, the needle valve, the gas flowmeter, the electromagnetic valve, the three-way valve and the online analyzer are all known technologies in the field and are commercially available products.
In this embodiment, the sample reactor 32 and the reference reactor 33 are both provided with reaction cells, and the reaction cells are all provided with three-dimensional multi-symmetrical PT100 temperature sensors around, so that more accurate exothermic heat change conditions can be obtained, and the temperature of the reaction furnace can be accurately controlled. Sample reactor 32 input and reference reactor 33 input are equipped with pressure sensor real-time detection reactor pressure, reference business turn over material system A and sample business turn over material system B's gas inlet pipeline all is equipped with gas flowmeter, all be equipped with the solenoid valve on sample reactor 32 and the reference reactor 33 output pipeline, but central control system accurate control gas flow rate, reaction pressure and reaction mass dwell time, in addition reference business turn over material system A and sample business turn over material system B are equipped with accurate liquid charge pump, but through central control system accurate control liquid flow rate, reaction pressure and reaction dwell time.
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 example, 30% methanol aqueous solution was used as a solid catalyst (the main components of the catalyst were CuO, ZnO and Al)2O3、Na2O) to generate hydrogen and carbon dioxide by a cracking reaction under catalysis, and the calorimetric test method is explained and further verified by bond energy calculation. 30% aqueous methanol solution at 0.0011g · s-1The flow rate is set to be 250-350 ℃, the material retention time is 15-20s, and the reaction pressure is 1.0 Mpa.
The test steps are as follows:
1) and (6) calibrating. Integrating the voltage peak area obtained from each pulse with the given power of 10mW in 2100s and each cycle time of 5400s, waiting for the return of the calorimetric signal at the initial baselineQiThe calibration temperature range is 150-450 ℃.
Time t of each pulse is 2100s
The given power P of each pulse is 10mW
Obtaining the sensitivity a under different temperature and different cycles according to the formula 1iFitting the sensitivities at different temperatures (see fig. 2), and obtaining sensitivity coefficients according to the fitting curves, wherein the sensitivity coefficients are respectively as follows:
b1=+5.543711E+0
b2=+4.186064E-3
b3=-3.4424099E-5
b4=+5.288008E-8
b5=-3.001592E-11
2) 150 ℃ and 450 ℃ sensitivity ai(T) the polynomial is:
ai(T)=(5.543711E+0)+(4.186064E-3)T+(-3.4424099E-5)T2+(5.288008E-8)T3+(-3.001592E-11)T4
3) and (3) performing airtight experiment on the reaction system. Introducing nitrogen into the sample and the reference reaction system through a feeding system, controlling the pressure of the nitrogen through a decompression meter, stopping introducing the nitrogen when the pressure of the introduced nitrogen reaches 3.0MPa, and performing pressure maintaining test, wherein if the pressure drop of the reactor system is less than 0.01 within 1h
bar·min-1When the reaction system was sealed, the reaction system was considered to have good airtightness, and the pressure holding was completed.
4) And (5) pressure relief. The solenoid valve was opened to vent the pressure to 0.1 MPa.
5) 3.5g of solid catalyst was added to the sample reactor, the catalyst loading amounted to 90-95% of the total volume of the test cell, and the sample reactor was connected to the reactor system after the addition.
6) The reactor heating system was started. Setting 2 K.min-1Raising the temperature to 300 ℃, and keeping the temperature constant.
7) Feeding. When the temperature in the reactor heating furnace is stabilized, the reference liquid feeding pump A14 and the sample liquid feeding pump B24 are controlled at 0.0011 g.s-1Pumping 30% methanol water solution into the sample reactor and the reference reactor at the same time at the flow rateThe methanol reacts under the action of the solid catalyst in the sample reactor, and the methanol in the reference system passes through and is discharged from the reference pool.
8) And acquiring data, namely acquiring the furnace temperature and the voltage signal change in the reactor on line in real time through a temperature sensor and a voltage signal sensor (see fig. 3), reading the voltage signal deviation baseline value △ U, acquiring the system pressure change through the pressure sensor, acquiring all data in real time through a central control system, and recording the experimental phenomenon until the experiment is finished.
9) And (5) cleaning and purging the reactor system after the experiment is finished.
10) The voltage signal is integrated off baseline △ U with area S (in mV. S)
11)t0=3.2h=11520s;
12)S=2.03492E+07μV·s
13) Sensitivity ai(T=300℃)=3.351779μW·mW-1
14) Substituting all values into equation (4) and calculating the exotherm Q of the reaction processt0Is 6.07116KJ
15) The mass flow rate of 30% methanol aqueous solution is 0.0011 g.s-1The apparent molar heat of reaction in the course of the reaction is calculated as methanol
16)W=3.8016g
17)M=32.04g·mol-1
18) The molar weight of the methanol is n calculated by the formula (4)0Is 0.1187mol
19) The obtained methanol hydrogen production molar reaction heat is-51.1 kJ.mol-1(in moles of methanol) (does not contain latent heat of vaporization and sensible heat of feed).
20) And (5) verifying the result. The heat of reaction in the molar range of-49.5 kJ. mol for producing hydrogen from methanol is described in the literature-1The error of the reaction heat obtained by the method from the value reported in the literature is 3.5 percent (calculated by the mole number of the methanol) and is not more than 5 percent.
In the above examples, 30% methanol aqueous solution was used in the presence of a solid catalyst (the catalyst mainly comprises CuO, ZnO and Al)2O3、Na2O) is catalyzed to generate hydrogen and carbon dioxideThe device and the test method are verified, and the apparent reaction heat obtained by the continuous flow reaction heat test method by using the reference heat is credible in heat treatment; and further can be applied to various calorimetric tests for obtaining tubular reaction gas-solid and gas-liquid phase continuous flow reaction through constant temperature or scanning temperature rising modes.