CN116793890B - Construction method of reaction kinetic model of supercritical CO2 pyrolysis kerogen experiment device - Google Patents
Construction method of reaction kinetic model of supercritical CO2 pyrolysis kerogen experiment device Download PDFInfo
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Abstract
The invention discloses a method for constructing a reaction kinetic model of a supercritical CO2 pyrolysis kerogen experiment device, and relates to the technical field of oil shale pyrolysis; the invention comprises a high-pressure thermogravimetric analyzer, a mass spectrometer, a water tank and supercritical CO 2 The device comprises a gas cylinder, an argon gas cylinder, a valve, a gas mass flowmeter and a digital collecting processor, wherein a mass spectrometer is positioned at the left side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer; in the invention, compared with a method of designing a high-temperature high-pressure pyrolysis oil shale test device by adopting a tubular furnace, the pressure ratio in the pyrolysis oil shale process is better controlled, and in addition, the high-pressure thermogravimetric analyzer adopts high-temperature supercritical CO 2 The atmosphere of the sweeping gas can timely take away pyrolysis products in different stages in the device, so that the pyrolysis products are effectively prevented from being subjected to secondary pyrolysis in the experimental device, and the experimental result, the parameters of reaction dynamics and the model are more accurate.
Description
Technical Field
The invention relates to the technical field of oil shale pyrolysis, in particular to a method for constructing a reaction kinetic model of a supercritical CO2 pyrolysis kerogen experiment device.
Background
The world oil shale reserves are abundant and widely distributed, the exploration and exploitation of the oil shale has important strategic significance, the oil shale is sedimentary rock which is very fine in particles and contains a large amount of immature organic matters or kerogen, the oil shale is heated to about 500 ℃, the kerogen is pyrolyzed to generate shale oil which is similar to petroleum, the oil shale reserves are abundant in the global scope and can be used as alternative energy sources, the oil gas exploration and development process is accelerated nowadays, the residual reserves of conventional oil gas are greatly reduced, and the oil shale is an important supplement of the conventional oil gas;
the pyrolysis of the oil shale is a complex multiphase chemical process, the variety of products is various, the thermal decomposition kinetics and the thermal decomposition mechanism are difficult to determine, at present, related scholars research the influence on the pyrolysis kinetics and thermodynamics of the oil shale under different atmospheres, different heating rates and different pressures and the like by taking the oil shale with different deposition characteristics at home and abroad as a test raw material, so that the oil production and gas production efficiency of the pyrolysis of the oil shale is improved, the kinetics of the pyrolysis of the oil shale can judge the difficulty of the pyrolysis reaction of the oil shale, and guidance and evaluation are given to the pyrolysis of the oil shale in theory;
the research of the kerogen is biased to the regular research of the adsorption and migration of the kerogen to the gas and the product characteristic mechanism research of the pyrolysis of the kerogen, the related experiments of the pyrolysis of the kerogen by high-temperature high-pressure gas are less, and most of the experiments are carried out through numerical simulation;
supercritical CO at present 2 Pyrolysis is less studied in the petroleum field, for example CN218811531U discloses a novel supercritical CO 2 Pyrolysis oil shale experimental setup, CN114525148A discloses a flexible pyrolysis system and method, but high temperature supercritical CO is not yet involved at present 2 Reaction kinetics research of pyrolysis oil shale;
the existing paper: supercritical CO 2 Numerical simulation and experimental research of pyrolysis oil shale are carried out by adopting a combined technology of a thermogravimetric analyzer and a differential scanning calorimeterInvestigation of nitrogen and CO 2 The influence of atmosphere on the pyrolysis of the oil shale, the control mechanism and the kinetic parameters of the pyrolysis reaction of the oil shale are obtained, a high-temperature high-pressure pyrolysis oil shale test device is designed through a tube furnace, and high-temperature high-pressure nitrogen and supercritical CO are carried out 2 The method comprises the steps of (1) carrying out an experiment of pyrolyzing the oil shale, and analyzing a gas sample and an oil sample acquired by the experiment by adopting a means of combining gas chromatography and mass spectrometry;
however, the prior art has the following problems:
the high-pressure thermogravimetric analyzer can meet the requirement of CO 2 The equipment with the purge gas in a high-temperature supercritical state is used for the related oil shale pyrolysis experiment, and only the pyrolysis atmosphere is referred to as the high-temperature purge gas by adopting a thermogravimetric analyzer;
1. the prior high-temperature high-pressure pyrolysis oil shale test device is designed through a tube furnace, free gas existing in original pores of the oil shale is separated out in the pyrolysis oil shale test process, and methane, ethane, propane, hydrogen, ethylene, propylene and the like are also released during kerogen pyrolysis along with the temperature rise. However, the device is airtight and is not a purging atmosphere, and pyrolysis products cannot be taken away in time, so that free methyl, hydrogen free radicals, hydroxyl and the like generated by kerogen pyrolysis in an airtight reaction system continuously participate in complex synthesis and decomposition reactions, and experimental errors are larger;
2. in addition, because of the secondary pyrolysis, more hydrocarbon components are released in the reaction kettle, the pressure system continuously fluctuates, and the pyrolysis pressure fluctuation degree is different under different atmospheres. CO at the same time 2 The pressure of the gas can not reach the requirement of the supercritical state, and the CO is designed 2 The output pressure of the steel cylinder is P, and the steel cylinder is at the temperature of the test systemThe volume of the high-temperature high-pressure reaction kettle is a constant value, and the pressure of the high-temperature high-pressure reaction kettle is directly controlled by the temperature. The pyrolysis experiment time is long, and the fluctuation time of a pressure system cannot be determined, so that the pressure control of the experiment is difficult;
in order to solve the problems, the inventor provides a method for constructing a reaction dynamics model of a supercritical CO2 pyrolysis kerogen experiment device.
Disclosure of Invention
In order to solve the problems that the error of the experimental result is large and the pressure control of the experiment is difficult; the invention aims to provide a method for constructing a reaction kinetic model of a supercritical CO2 pyrolysis kerogen experiment device.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for constructing a reaction kinetic model of a supercritical CO2 pyrolysis kerogen experiment device comprises a high-pressure thermogravimetric analyzer, a mass spectrometer, a water tank and supercritical CO 2 The gas cylinder, the argon gas cylinder, the valve, the gas mass flowmeter and the digital collecting processor, wherein the mass spectrometer is positioned at the left side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the digital collecting processor is positioned at the left upper side of the high-pressure thermogravimetric analyzer and is respectively connected with the high-pressure thermogravimetric analyzer and the mass spectrometer, the water tank is positioned at the right side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the gas mass flowmeter is positioned at the right upper side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the lower part of the gas mass flowmeter is connected with the valve, and the supercritical CO is used for collecting the gas 2 The gas cylinder and the argon gas cylinder are positioned at the upper right part of the high-pressure thermogravimetric analyzer and are connected with the gas mass flowmeter through a valve, and the supercritical CO 2 The gas cylinder is located the left side of argon gas cylinder and is connected with the argon gas cylinder.
Preferably, a display is connected to the upper side of the high-pressure thermogravimetric analyzer in a signal manner, and a reaction cabin is arranged on the left side of the high-pressure thermogravimetric analyzer.
Supercritical CO 2 The method for constructing the reaction kinetic model of the pyrolysis kerogen experiment device comprises the following steps:
s1, opening a water tank switch of the high-pressure thermogravimetric analyzer in sequence from left to right, and setting the temperature of the water tank
Opening a valve of an argon gas bottle and a gas mass flowmeter, regulating the gas flow, introducing argon one day before experiment development, and discharging air in a pipeline of experimental equipment, thereby reducing errors and connectingPipeline connected to high pressure thermogravimetric analyzer and mass spectrometer, high temperature supercritical CO 2 The pyrolysis kerogen is tested by adopting a high-pressure thermogravimetric analyzer and a mass spectrometer;
s2, closing an argon cylinder valve, and opening supercritical CO 2 Valve of gas cylinder and gas mass flowmeter
In testing high temperature supercritical CO 2 Before pyrolyzing kerogen, a white control experiment is required to be carried out, an unfilled crucible is placed on a sensor by using tweezers, a blank crucible is placed on a left circle of the sensor, a sample crucible is placed on a right circle of the sensor, a Tare key on a display is used for adjusting the sensor, furnace is selected to open and close a cabin door of a reaction cabin, protective gas is injected to the experimental pressure, the initial temperature, the heating speed and the reaction end temperature of a high-pressure thermogravimetric analyzer are set by a data collection analyzer, and the purge gas is set to be supercritical CO 2 The gas injection rate in the test is precisely controlled by a gas mass flowmeter connected with the high-pressure reaction tank, after the experiment is finished, the reaction cabin is waited to be reduced to a proper temperature, the cabin door is opened, the crucible is taken out by forceps, and the experiment can be carried out again after the temperature is reduced to the room temperature;
s3, sealing the experimental oil shale sample into paraffin to prevent weathering and degradation
Separating and extracting kerogen from oil shale by adopting a physical and chemical combination method according to a two-part rinsing and one-step alkali washing method, drying the obtained kerogen, filling into a sample bag, weighing a proper amount of sample of the kerogen by forceps for subsequent test analysis experiments, placing the sample in a crucible, wherein the mass of the sample is not more than 10mg, repeating S2, and developing high-temperature supercritical CO at different heating rates 2 Pyrolyzing kerogen experiments;
s4, pyrolysis is divided into a physical stage and a chemical stage, wherein the chemical stage comprises two processes of pyrolysis and coke dehydrogenation, experimental data are processed, and high-temperature supercritical CO is analyzed 2 During the pyrolysis of kerogen
The thermal gravimetric curve and the differential thermal gravimetric curve of the kerogen are obtained through a high-pressure thermal gravimetric analyzer, a mass spectrometer can obtain products of the pyrolysis process, the two can be combined to obtain the thermal gravimetric-differential thermal gravimetric curves of the temperature, the products and the products of different reaction stages, the thermal gravimetric-differential thermal gravimetric curves of the products of different reaction stages are analyzed, the thermal decomposition stage weightlessness and conversion rate characteristics under the condition of different heating rates are analyzed, and thermal decomposition characteristic parameters are obtained, wherein the method comprises the following steps: the method comprises the steps of starting pyrolysis temperature, ending pyrolysis temperature, maximum pyrolysis weight loss rate, temperature corresponding to the maximum pyrolysis weight loss rate and pyrolysis conversion rate corresponding to the final temperature;
s5, establishing a reaction dynamics model
As can be known from the calculation of a DAEM model, a Doyle method and a FWO method, E increases along with the increase of the conversion rate in the pyrolysis process of the oil shale, the E obtained by the DAEM model and the FWO method is relatively close, the decision coefficient of the DAEM model is the highest, and the DAEM model is adopted for high-temperature supercritical CO 2 Solving and analyzing thermal gravimetric experimental data of pyrolytic kerogen at different heating rates to obtain key kinetic parameters such as apparent reaction activation energy, pre-finger factors and the like, thereby establishing a reaction kinetic model.
Preferably, for the decomposition reaction, the decomposition rate can be expressed as:
arrhenius equation integral:
wherein: k (k) 0 Is the factor before finger, S -1 The method comprises the steps of carrying out a first treatment on the surface of the Ea is activation energy, kJ/mol; t is the thermodynamic temperature, K; r is a gas constant, so the overall reaction equation for pyrolysis of oil shale can be expressed as:
rate of temperature rise under non-isothermal conditionsSubstituting the above formula to obtain:
wherein: the functional form of f (α) includes the number of reaction stages therein, which is determined by the type of reaction or the mechanism of reaction, and is usually f (α) = (1-a) n Since the sample used in the experiment is kerogen with the particle diameter below 74 mu m, the molar concentration gradient and the temperature gradient inside the particles in the process of the pyrolysis reaction of the kerogen are negligible, and the reaction equation can be regarded as an intrinsic reaction dynamics equation.
Preferably, the DAEM model solving process is as follows:
i) The activation energy distribution assumes that apparent activation energy is a continuous function of temperature, and each stage of reaction has a certain value of apparent activation energy;
II) parallel reactions are called different reactions taking the same substance or the same plurality of substances as reactants and simultaneously taking place, wherein in the parallel reactions, the same reactant participates in different reactions to generate different products, a plurality of reactions exist in organic reactions, the side reactions exist, the parallel reactions exist, and the high temperature supercritical CO 2 The shale oil, the carbonization gas and the semicoke products are generated in the process of pyrolyzing the kerogen, and the main components generated by pyrolysis are alkane and olefin compounds, so that the aromatic compounds have low yield, and the rest are hetero-atom long-chain fatty acids and the like, and can be considered as different products of parallel reaction;
III) Infinite parallel reaction assumption is a reaction system which allows a large number of independent first-order reactions, wherein the first-order reactions are formed by the fact that the reaction rate is only in direct proportion to the first power of the concentration of substances, the activation energy of each stage of reactions is different, the process of pyrolyzing kerogen consists of a plurality of independent irreversible reactions, the two assumption are satisfied, and the high-temperature supercritical CO 2 The pyrolytic kerogen process can be regarded as a primary kinetic reaction and can be expressed as:
wherein: Δa is the pyrolytic conversion per moment,%; Δa * At E for activation energy a ～～(E a +ΔE a ) The pyrolysis conversion percent of (c) is further deduced as:
wherein: w (w) t And w 0 Sample masses at time t and initial time respectively; w (w) t /(w 0 -w ∞ ) Is the conversion rate alpha; k (k) 0 Is a pre-finger factor; beta is the temperature rising rate; ea is apparent activation energy; r is an ideal gas constant; t is the sample temperature; f (Ea) is an apparent activation energy distribution function;
VI) in the temperature programming with a temperature increase rate β, t=t 0 +β, i.e.The step approximation function is adopted to sort the materials:
v) considering the error in the dynamics test, calculating the reaction activation energy and the pre-finger factor only from two-point dynamics data often brings about larger error, generally, by measuring the reaction rate constants at a plurality of temperatures to fit the reaction activation energy and the pre-finger factor, a linear regression method can be adopted to estimate the activation energy by utilizing the multi-point experimental data, the Arrhenius of the first-order dynamics reaction is a straight line, and under the same pyrolysis conversion rate, whether temperature programming or constant-temperature pyrolysis is carried out, the method comprises the following steps ofAnd->Arrhenius straight line at the same conversion rate on the plate, apparent activation energy Ea of key kinetic parameters and pre-finger factor k 0 Can be calculated by the slope and intercept of the straight line corresponding to each conversion rate alpha.
Preferably, the CMG software is used for establishing a 0-dimensional value simulation model for simulating high-temperature supercritical CO at different heating rates 2 Pyrolyzing kerogen experiment, comparing the composition characteristics of the simulation product and the experimental product, adjusting the reaction kinetic parameters in the numerical simulation model, and establishing high-temperature supercritical CO which can be used for multiple scale numerical simulation research 2 And (5) pyrolyzing an intrinsic reaction kinetic model.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the output of oil gas can be effectively simulated, and the pyrolysis reaction kinetics is not involved;
2. in the invention, the experimental method adopts the high-pressure thermogravimetric analyzer, can simultaneously meet the experimental environment of high temperature and high pressure, and has wider applicable experimental conditions than the thermogravimetric analyzer;
3. in the invention, compared with a method of designing a high-temperature high-pressure pyrolysis oil shale test device by adopting a tubular furnace, the pressure ratio in the pyrolysis oil shale process is better controlled, and in addition, the high-pressure thermogravimetric analyzer adopts high-temperature supercritical CO 2 The atmosphere of the purge gas can timely take away pyrolysis products in different stages in the device, so that the pyrolysis products are effectively prevented from being subjected to secondary pyrolysis in the experimental device, and the experimental result, the parameters of reaction dynamics and the model are more accurate;
4. in the invention, the DAEM model is more suitable for dynamic analysis of oil shale pyrolysis in 3 thermodynamic analysis methods by comparing the DAEM model, the Doyle method and the FWO method, the reaction dynamic model established by combining the parallel reaction model can better reflect the pyrolysis process of the oil shale, and the high-temperature supercritical CO which can be used for numerical simulation research of various scales is established by adjusting the reaction dynamic parameters in the numerical simulation model by comparing the composition characteristics of simulation products and experimental products 2 And (5) pyrolyzing an intrinsic reaction kinetic model.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of the connection structure of the device of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. 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.
Examples: as shown in FIG. 1, the invention provides a method for constructing a reaction kinetic model of a supercritical CO2 pyrolysis kerogen experiment device, which comprises a high-pressure thermogravimetric analyzer, a mass spectrometer, a water tank and supercritical CO 2 The gas cylinder, the argon gas cylinder, the valve, the gas mass flowmeter and the digital collecting processor, wherein the mass spectrometer is positioned at the left side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the digital collecting processor is positioned at the left upper side of the high-pressure thermogravimetric analyzer and is respectively connected with the high-pressure thermogravimetric analyzer and the mass spectrometer, the water tank is positioned at the right side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the gas mass flowmeter is positioned at the right upper side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the lower part of the gas mass flowmeter is connected with the valve, and the supercritical CO is used for collecting the gas 2 The gas cylinder and the argon gas cylinder are positioned at the upper right part of the high-pressure thermogravimetric analyzer and are connected with the gas mass flowmeter through a valve, and the supercritical CO 2 The gas cylinder is located the left side of argon gas cylinder and is connected with the argon gas cylinder.
The upper signal of the high-pressure thermogravimetric analyzer is connected with a display, and the left side of the high-pressure thermogravimetric analyzer is provided with a reaction cabin.
The invention also provides supercritical CO 2 The method for constructing the reaction kinetic model of the pyrolysis kerogen experiment device comprises the following steps:
s1, opening a water tank switch of the high-pressure thermogravimetric analyzer in sequence from left to right, and setting the temperature of the water tank
Opening a valve of an argon gas bottle and a gas mass flowmeter, regulating the gas flow, introducing argon the day before the experiment is carried out, and discharging air in a pipeline of experimental equipment, thereby reducing errors, connecting the pipeline of a high-pressure thermogravimetric analyzer and a mass spectrometer, and connecting high-temperature supercritical CO 2 The pyrolysis kerogen is tested by adopting a high-pressure thermogravimetric analyzer and a mass spectrometer;
s2, closing an argon cylinder valve, and opening supercritical CO 2 Valve of gas cylinder and gas mass flowmeter
In testing high temperature supercritical CO 2 Before pyrolyzing kerogen, a white control experiment is required to be carried out, an unfilled crucible is placed on a sensor by using tweezers, a blank crucible is placed on a left circle of the sensor, a sample crucible is placed on a right circle of the sensor, a Tare key on a display is used for adjusting the sensor, furnace is selected to open and close a cabin door of a reaction cabin, protective gas is injected to the experimental pressure, the initial temperature, the heating speed and the reaction end temperature of a high-pressure thermogravimetric analyzer are set by a data collection analyzer, and the purge gas is set to be supercritical CO 2 The gas injection rate in the test is precisely controlled by a gas mass flowmeter connected with the high-pressure reaction tank, after the experiment is finished, the reaction cabin is waited to be reduced to a proper temperature, the cabin door is opened, the crucible is taken out by forceps, and the experiment can be carried out again after the temperature is reduced to the room temperature;
s3, sealing the experimental oil shale sample into paraffin to prevent weathering and degradation
Separating and extracting kerogen from oil shale by adopting a physical and chemical combination method according to a two-part rinsing and one-step alkali washing method, drying the obtained kerogen, filling into a sample bag, weighing a proper amount of sample of the kerogen by forceps for subsequent test analysis experiments, placing the sample in a crucible, wherein the mass of the sample is not more than 10mg, repeating S2, and developing high-temperature supercritical CO at different heating rates 2 Pyrolyzing kerogen experiments;
s4, pyrolysis is divided into a physical stage and a chemical stage, wherein the chemical stage comprises two processes of pyrolysis and coke dehydrogenation, experimental data are processed, and high-temperature supercritical CO is analyzed 2 During the pyrolysis of kerogen
The thermal gravimetric curve and the differential thermal gravimetric curve of the kerogen are obtained through a high-pressure thermal gravimetric analyzer, a mass spectrometer can obtain products of the pyrolysis process, the two can be combined to obtain the thermal gravimetric-differential thermal gravimetric curves of the temperature, the products and the products of different reaction stages, the thermal gravimetric-differential thermal gravimetric curves of the products of different reaction stages are analyzed, the thermal decomposition stage weightlessness and conversion rate characteristics under the condition of different heating rates are analyzed, and thermal decomposition characteristic parameters are obtained, wherein the method comprises the following steps: the method comprises the steps of starting pyrolysis temperature, ending pyrolysis temperature, maximum pyrolysis weight loss rate, temperature corresponding to the maximum pyrolysis weight loss rate and pyrolysis conversion rate corresponding to the final temperature;
s5, establishing a reaction dynamics model
As can be known from the calculation of a DAEM model, a Doyle method and a FWO method, E increases along with the increase of the conversion rate in the pyrolysis process of the oil shale, the E obtained by the DAEM model and the FWO method is relatively close, the decision coefficient of the DAEM model is the highest, and the DAEM model is adopted for high-temperature supercritical CO 2 Solving and analyzing thermal gravimetric experimental data of pyrolytic kerogen at different heating rates to obtain key kinetic parameters such as apparent reaction activation energy, pre-finger factors and the like, thereby establishing a reaction kinetic model.
For the decomposition reaction, the decomposition rate can be expressed as:
arrhenius equation integral:
wherein: k (k) 0 Is the factor before finger, S -1 The method comprises the steps of carrying out a first treatment on the surface of the Ea is activation energy, kJ/mol; t is the thermodynamic temperature, K; r is a gas constant, so the overall reaction equation for pyrolysis of oil shale can be expressed as:
rate of temperature rise under non-isothermal conditionsSubstituting the above formula to obtain:
wherein: the functional form of f (α) includes the number of reaction stages therein, which is determined by the type of reaction or the mechanism of reaction, and is usually f (α) = (1-a) n Since the sample used in the experiment is kerogen with the particle diameter below 74 mu m, the molar concentration gradient and the temperature gradient inside the particles in the process of the pyrolysis reaction of the kerogen are negligible, and the reaction equation can be regarded as an intrinsic reaction dynamics equation.
The DAEM model solving process is as follows:
i) The activation energy distribution assumes that apparent activation energy is a continuous function of temperature, and each stage of reaction has a certain value of apparent activation energy;
II) parallel reactions are called different reactions taking the same substance or the same plurality of substances as reactants and simultaneously taking place, wherein in the parallel reactions, the same reactant participates in different reactions to generate different products, a plurality of reactions exist in organic reactions, the side reactions exist, the parallel reactions exist, and the high temperature supercritical CO 2 The shale oil, the carbonization gas and the semicoke products are generated in the process of pyrolyzing the kerogen, and the main components generated by pyrolysis are alkane and olefin compounds, so that the aromatic compounds have low yield, and the rest are hetero-atom long-chain fatty acids and the like, and can be considered as different products of parallel reaction;
III) Infinite parallel reaction assumption is a reaction system which allows a large number of independent first-order reactions, wherein the first-order reactions are formed by the fact that the reaction rate is only in direct proportion to the first power of the concentration of substances, the activation energy of each stage of reactions is different, the process of pyrolyzing kerogen consists of a plurality of independent irreversible reactions, the two assumption are satisfied, and the high-temperature supercritical CO 2 The pyrolytic kerogen process can be regarded as a primary kinetic reaction and can be expressed as:
wherein: Δa is the pyrolytic conversion per moment,%; Δa * At E for activation energy a ～～(E a +ΔE a ) The pyrolysis conversion percent of (c) is further deduced as:
wherein: wt and w0 are the sample masses at time t and initial time, respectively; wt/(w 0-w infinity) is the conversion α; k0 is a pre-finger factor; beta is the temperature rising rate; ea is apparent activation energy; r is an ideal gas constant; t is the sample temperature; f (Ea) is an apparent activation energy distribution function;
VI) in the temperature programming with a temperature increase rate β, t=t 0 +β, i.e.The step approximation function is adopted to sort the materials:
v) considering the error in the dynamics test, calculating the reaction activation energy and the pre-finger factor only from two-point dynamics data often brings about larger error, generally, by measuring the reaction rate constants at a plurality of temperatures to fit the reaction activation energy and the pre-finger factor, a linear regression method can be adopted to estimate the activation energy by utilizing the multi-point experimental data, the Arrhenius of the first-order dynamics reaction is a straight line, and under the same pyrolysis conversion rate, whether temperature programming or constant-temperature pyrolysis is carried out, the method comprises the following steps ofAnd->Arrhenius straight line at the same conversion rate on the plate, and apparent activation energy E of key kinetic parameters a And pre-finger factor k 0 Can be calculated by the slope and intercept of the straight line corresponding to each conversion rate alpha.
Establishing a 0-dimensional value simulation model by using CMG software to simulate high-temperature supercritical CO at different heating rates 2 Pyrolyzing kerogen experiment, comparing the composition characteristics of the simulation product and the experimental product, adjusting the reaction kinetic parameters in the numerical simulation model, and establishing high-temperature supercritical CO which can be used for multiple scale numerical simulation research 2 And (5) pyrolyzing an intrinsic reaction kinetic model.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (2)
1. A method for constructing a reaction kinetic model of a supercritical CO2 pyrolysis kerogen experiment device comprises the following steps of adopting an experiment device comprising a high-pressure thermogravimetric analyzer, a mass spectrometer, a water tank and supercritical CO 2 Gas cylinder, argon gas cylinder, valve, gas mass flowmeter and digital collection processor, its characterized in that: the mass spectrometer is positioned at the left side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the digital collecting processor is positioned at the upper left side of the high-pressure thermogravimetric analyzer and is respectively connected with the high-pressure thermogravimetric analyzer and the mass spectrometer, the water tank is positioned at the right side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the gas mass flowmeter is positioned at the upper right side of the high-pressure thermogravimetric analyzer and is connected with the high-pressure thermogravimetric analyzer, the lower part of the gas mass flowmeter is connected with the valve, and the supercritical CO is obtained by the method of the mass spectrometer 2 The gas cylinder and the argon gas cylinder are positioned at the upper right part of the high-pressure thermogravimetric analyzer and are connected with the gas mass flowmeter through a valve, and the supercritical CO 2 The gas cylinder is positioned at the left side of the argon gas cylinder and is connected with the argon gas cylinder;
a display is connected with the upper part of the high-pressure thermogravimetric analyzer in a signal way, and a reaction cabin is arranged on the left side of the high-pressure thermogravimetric analyzer;
the construction method comprises the following steps:
s1, opening a water tank switch of the high-pressure thermogravimetric analyzer according to the sequence from left to right, setting the temperature of the water tank, opening a valve of an argon gas cylinder and a gas mass flowmeter, adjusting the gas flow, introducing argon one day before experiment development, and discharging air in a pipeline of experimental equipment, thereby reducing errors, connecting the pipeline of the high-pressure thermogravimetric analyzer and a pipeline of a mass spectrometer, and connecting high-temperature supercritical CO 2 The pyrolysis kerogen is tested by adopting a high-pressure thermogravimetric analyzer and a mass spectrometer;
s2, closing an argon cylinder valve, and opening supercritical CO 2 Valve of gas cylinder and gas mass flowmeter
In testing high temperature supercritical CO 2 Before pyrolyzing kerogen, a white control experiment is required to be carried out, an unfilled crucible is placed on a sensor by using tweezers, a blank crucible is placed on a left circle of the sensor, a sample crucible is placed on a right circle of the sensor, a Tare key on a display is used for adjusting the sensor, furnace is selected to open and close a cabin door of a reaction cabin, protective gas is injected to the experimental pressure, the initial temperature, the heating speed and the reaction end temperature of a high-pressure thermogravimetric analyzer are set by a data collection analyzer, and the purge gas is set to be supercritical CO 2 The gas injection rate in the test is precisely controlled by a gas mass flowmeter connected with the high-pressure reaction tank, after the experiment is finished, the reaction cabin is waited to be reduced to a proper temperature, the cabin door is opened, the crucible is taken out by forceps, and the experiment can be carried out again after the temperature is reduced to the room temperature;
s3, sealing the experimental oil shale sample into paraffin to prevent weathering and degradation
Separating and extracting kerogen from oil shale by adopting a physical and chemical combination method according to a two-part rinsing and one-step alkali washing method, drying the obtained kerogen, filling into a sample bag, weighing a proper amount of sample of the kerogen by forceps for subsequent test analysis experiments, placing the sample in a crucible, wherein the mass of the sample is not more than 10mg, repeating S2, and developing high-temperature supercritical CO at different heating rates 2 Pyrolyzing kerogen experiments;
s4, heatThe decomposition is divided into a physical stage and a chemical stage, wherein the chemical stage comprises two processes of pyrolysis and coke dehydrogenation, experimental data are processed, and high-temperature supercritical CO is analyzed 2 During the pyrolysis of kerogen
The thermal gravimetric curve and the differential thermal gravimetric curve of the kerogen are obtained through a high-pressure thermal gravimetric analyzer, a mass spectrometer can obtain products of the pyrolysis process, the two can be combined to obtain the thermal gravimetric-differential thermal gravimetric curves of the temperature, the products and the products of different reaction stages, the thermal gravimetric-differential thermal gravimetric curves of the products of different reaction stages are analyzed, the thermal decomposition stage weightlessness and conversion rate characteristics under the condition of different heating rates are analyzed, and thermal decomposition characteristic parameters are obtained, wherein the method comprises the following steps: the method comprises the steps of starting pyrolysis temperature, ending pyrolysis temperature, maximum pyrolysis weight loss rate, temperature corresponding to the maximum pyrolysis weight loss rate and pyrolysis conversion rate corresponding to the final temperature;
s5, establishing a reaction dynamics model
As can be known from the calculation of a DAEM model, a Doyle method and a FWO method, E increases along with the increase of the conversion rate in the pyrolysis process of the oil shale, the E obtained by the DAEM model and the FWO method is relatively close, the decision coefficient of the DAEM model is the highest, and the DAEM model is adopted for high-temperature supercritical CO 2 Solving and analyzing thermal gravimetric experimental data of pyrolyzed kerogen at different heating rates to obtain key kinetic parameters such as apparent reaction activation energy, pre-finger factors and the like, thereby establishing a reaction kinetic model;
for the decomposition reaction, the decomposition rate can be expressed as:
arrhenius equation integral:
wherein: k (k) 0 Is the factor before finger, S -1 The method comprises the steps of carrying out a first treatment on the surface of the Ea is activation energy, kJ/mol; t is the thermodynamic temperature, K; r is a gas constant, so the overall reaction equation for pyrolysis of oil shale can be expressed as:
rate of temperature rise under non-isothermal conditionsSubstituting the above formula to obtain:
wherein: the functional form of f (α) includes the number of reaction stages therein, which is determined by the type of reaction or the mechanism of reaction, and is usually f (α) = (1-a) n Because the sample used in the experiment is kerogen with the particle diameter below 74 mu m, the molar concentration gradient and the temperature gradient in the particle can be ignored in the process of the pyrolysis reaction of the kerogen, and the reaction equation can be regarded as an intrinsic reaction kinetic equation;
the DAEM model solving process is as follows:
i) The activation energy distribution assumes that apparent activation energy is a continuous function of temperature, and each stage of reaction has a certain value of apparent activation energy;
II) parallel reactions are called different reactions taking the same substance or the same plurality of substances as reactants and simultaneously taking place, wherein in the parallel reactions, the same reactant participates in different reactions to generate different products, a plurality of reactions exist in organic reactions, the side reactions exist, the parallel reactions exist, and the high temperature supercritical CO 2 The shale oil, the carbonization gas and the semicoke products are generated in the process of pyrolyzing the kerogen, and the main components generated by pyrolysis are alkane and olefin compounds, so that the aromatic compounds have low yield, and the rest are hetero-atom long-chain fatty acids and the like, and can be considered as different products of parallel reaction;
III) Infinite parallel reaction is assumed to be a reaction system which allows a large number of independent first-order reactions, wherein the first-order reaction is that the reaction rate is only proportional to the first power of the concentration of substances, the activation energy of each-stage reaction is different, and the kerogen is pyrolyzedThe process of (2) consists of a plurality of independent irreversible reactions, meets the two assumptions, and is high-temperature supercritical CO 2 The pyrolytic kerogen process can be regarded as a primary kinetic reaction and can be expressed as:
wherein: Δa is the pyrolytic conversion per moment,%; Δa * At E for activation energy a ～～(E a +ΔE a ) The pyrolysis conversion percent of (c) is further deduced as:
wherein: w (w) t And w 0 Sample masses at time t and initial time respectively; w (w) t /(w 0 -w ∞ ) Is the conversion rate alpha; k (k) 0 Is a pre-finger factor; beta is the temperature rising rate; ea is apparent activation energy; r is an ideal gas constant; t is the sample temperature; f (Ea) is an apparent activation energy distribution function;
VI) in the temperature programming with a temperature increase rate β, t=t 0 +β, i.e.The step approximation function is adopted to sort the materials:
v) considering errors in kinetic tests, calculating the reaction activation energy and the pre-finger factor only from two-point kinetic data often brings about larger errors, generally fitting the reaction activation energy and the pre-finger factor by measuring reaction rate constants at a plurality of temperatures, estimating the activation energy by using multi-point experimental data can adopt a linear regression method, arrhenius of the first-order kinetic reaction is a straight line, and the same heat is generatedAt the conversion rate, whether the temperature is programmed or the pyrolysis is carried out at constant temperature, byAnd->Arrhenius straight line at the same conversion rate on the plate, and apparent activation energy E of key kinetic parameters a And pre-finger factor k 0 Can be calculated by the slope and intercept of the straight line corresponding to each conversion rate alpha.
2. The method for constructing a reaction kinetic model of a supercritical CO2 pyrolysis kerogen experiment device as claimed in claim 1, wherein a 0-dimensional value simulation model is established by CMG software to simulate high-temperature supercritical CO at different heating rates 2 Pyrolyzing kerogen experiment, comparing the composition characteristics of the simulation product and the experimental product, adjusting the reaction kinetic parameters in the numerical simulation model, and establishing high-temperature supercritical CO which can be used for multiple scale numerical simulation research 2 And (5) pyrolyzing an intrinsic reaction kinetic model.
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