CN107808019B - Method and system for establishing oil shale in-situ conversion temperature, time and conversion rate chart - Google Patents
Method and system for establishing oil shale in-situ conversion temperature, time and conversion rate chart Download PDFInfo
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- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
- E21B43/241—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection combined with solution mining of non-hydrocarbon minerals, e.g. solvent pyrolysis of oil shale
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Abstract
The invention discloses a method and a system for establishing a chart of in-situ conversion temperature, time and conversion rate of oil shale, wherein the method comprises the steps of selecting an oil shale sample from a planned exploitation area of the oil shale, and adopting a rock pyrolysis analyzer to perform an experiment on the oil shale sample; obtaining the relation data among pyrolysis activation energy, conversion rate and frequency factor according to the experimental result; and establishing a relation chart between the reciprocal of the in-situ conversion temperature of the oil shale and the logarithm of the time when the conversion rate is different values based on the relation data. By utilizing the method, the temperature and time of the in-situ conversion of the oil shale in the mining area can be rapidly known, and the conversion rate to which degree can be reached can be rapidly obtained, so that important parameters are provided for engineering decision and cost accounting.
Description
Technical Field
The invention belongs to the field of oil shale mining and research, and particularly relates to a method and a system for establishing a chart of oil shale in-situ conversion temperature, time and conversion rate.
Background
Oil shale is a high ash sedimentary rock containing combustible organic matter, mainly kerogen/kerogen. Organic matter (kerogen/kerogen) in oil shale can be pyrolyzed in the absence of air or oxygen, producing shale oil, retorting gas, solid carbonaceous residue, and a small amount of pyrolysis water. The global oil shale resource is quite rich, and the amount of the oil shale resource is about 10 trillion tons according to incomplete statistics, which is more than 50 percent more than the amount of the traditional oil resource (2710 trillion tons).
At present, there are two main ways for oil shale development: in-situ conversion mining and ground dry distillation. The ground dry distillation refers to that the oil shale is sent to the ground after open-pit mining or underground mining, is crushed and screened to the required granularity or lumpiness, enters a dry distillation furnace to be heated and dry distilled to produce shale oil gas and shale semicoke or shale ash. In-situ conversion exploitation refers to that oil shale buried underground is directly heated and retorted underground without exploitation, and produced shale oil gas is led out to the ground. Compared with ground dry distillation, the in-situ mining has the advantages of saving open-pit mining cost, reducing the damage degree of ground vegetation, occupying less area and the like.
For in-situ conversion exploitation of oil shale, the final temperature of heating, the heating time and the final oil-gas conversion rate are closely related, and the quality of oil gas and the production cost are closely related. In the prior art, the time and the cost of the method for obtaining the relation between the heating temperature of the oil shale and the time and the conversion rate are high, for example, the relation between the heating temperature of the oil shale with the mahogany zone and the heating time and the conversion rate is obtained in the field test of 160 acre zones in the state of colorado in 2003-2005 by shell company. Besides the field test technology, other in-situ mining technologies belonging to the concept stage try to establish the quantitative relation of the temperature-time-conversion rate of the oil shale by using an indoor physical simulation experiment, although some temperature-time-conversion rate information can be obtained, the biggest problem of the indoor physical simulation experiment is the simulation time scale, which is different from the ground destructive distillation of the oil shale, the in-situ destructive distillation conversion needs to realize conversion at a relatively low temperature by prolonging the heating time so as to reduce the production cost, and the indoor short-time experiment can only realize the conversion of oil shale into oil gas through a high temperature. Therefore, how to rapidly and quantitatively judge the relation between the oil shale in-situ conversion mining temperature-time-conversion rate and establish an oil shale in-situ conversion mining temperature-time-conversion rate chart is very important.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a method for rapidly and quantitatively determining the relationship between the oil shale in-situ conversion mining temperature-time-conversion rate and establishing an oil shale in-situ conversion mining temperature-time-conversion rate chart.
In order to solve the technical problems, the embodiment of the application firstly provides a method for establishing a chart of in-situ conversion temperature, time and conversion rate of oil shale, which comprises the steps of selecting an oil shale sample from an oil shale area to be mined, and carrying out an experiment on the oil shale sample by adopting a rock pyrolysis analyzer; obtaining the relation data among pyrolysis activation energy, conversion rate and frequency factor according to the experimental result; and establishing a relation chart between the reciprocal of the in-situ conversion temperature of the oil shale and the logarithm of the time when the conversion rate is different values based on the relation data.
Preferably, the obtaining of the relationship data between the pyrolysis activation energy, the conversion rate and the frequency factor according to the experimental result comprises: recording the variation data of the pyrolysis yield under different heating rates by using a rock pyrolysis analyzer; acquiring the corresponding relation between the pyrolysis hydrocarbon yield and the conversion rate according to the variation data of the pyrolysis yield; performing a simulation with a rock pyrolysis analyzer based on the variation data of the pyrolysis yield to determine a correspondence between pyrolysis activation energy and pyrolysis hydrocarbon yield; and establishing a relation curve of pyrolysis activation energy and conversion rate according to the corresponding relation between the pyrolysis hydrocarbon yield and the conversion rate and the corresponding relation between the pyrolysis activation energy and the pyrolysis hydrocarbon yield.
Preferably, the step of performing a simulation based on the variation data of the pyrolysis yield using a rock pyrolysis analyzer to determine a correspondence between pyrolysis activation energy and pyrolysis hydrocarbon yield further includes determining a correspondence between pyrolysis activation energy and a frequency factor.
Preferably, the establishing a chart of the relationship between the reciprocal of the in-situ conversion temperature of the oil shale and the logarithm of the time when the conversion rate is different values based on the relationship data comprises: establishing a linear model of the logarithm of the reciprocal of the temperature and the time for a fixed reaction degree or for different reactions of the same reaction degree according to the characteristics of the thermal cracking reaction with the first-order reaction characteristics; and substituting the relation data into the linear model to obtain a relation chart between the reciprocal of the temperature and the logarithm of the time when the conversion rate is different values.
Preferably, the characteristics of the thermal cracking reaction having the first order reaction characteristics are shown in the following expression:
wherein E represents the pyrolysis activation energy, T represents the temperature, T represents the time, R is the gas constant, and A is the constant to be determined.
Preferably, when the oil shale sample is tested by a rock pyrolysis analyzer, the method comprises the following steps: crushing the oil shale sample to enable the grain diameter of the oil shale sample to be between 0.07mm and 0.15 mm; a certain amount of sample is weighed every time, and the measurement data under different heating rates are recorded for multiple times.
Preferably, after establishing a chart of the relationship between the reciprocal of the in-situ conversion temperature of the oil shale and the logarithm of the time when the conversion rate is different, the method further comprises predicting the temperature, the time and the conversion rate of the in-situ conversion of the oil shale by using the chart of the relationship.
The embodiment of the present application further provides a system for creating a chart of in-situ conversion temperature, time and conversion rate of oil shale, which includes: the sample analysis module is used for selecting an oil shale sample from an oil shale area to be mined and carrying out an experiment on the oil shale sample by adopting a rock pyrolysis analyzer; the data acquisition module is used for acquiring relationship data among pyrolysis activation energy, conversion rate and frequency factors according to the experimental result; and the chart establishing module is used for establishing a chart of the relation between the reciprocal of the in-situ conversion temperature of the oil shale and the logarithm of the time when the conversion rate is different values based on the relation data.
Preferably, the plate establishing module establishes a plate of the relationship between the reciprocal of the in-situ conversion temperature of the oil shale and the logarithm of the time when the conversion rate is different values according to the following steps, and establishes a linear model of the reciprocal of the temperature and the logarithm of the time for a fixed reaction degree or different reactions with the same reaction degree according to the characteristics of the thermal cracking reaction with the first-order reaction characteristics; and substituting the relation data into the linear model to obtain a relation chart between the reciprocal of the temperature and the logarithm of the time when the conversion rate is different values.
Preferably, the characteristics of the thermal cracking reaction having the first order reaction characteristics are shown in the following expression:
wherein E represents the pyrolysis activation energy, T represents the temperature, T represents the time, R is the gas constant, and A is the constant to be determined.
Compared with the prior art, one or more embodiments in the above scheme can have the following advantages or beneficial effects:
a kinetic model is obtained by utilizing oil shale pyrolysis curves at different heating rates, and an oil shale in-situ conversion temperature-time-conversion rate chart is established according to a chemical kinetic principle, so that the temperature and time of the oil shale in-situ conversion in a mining area can be rapidly known, and important parameters are provided for engineering decision and cost accounting.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the technology or prior art of the present application and are incorporated in and constitute a part of this specification. The drawings expressing the embodiments of the present application are used for explaining the technical solutions of the present application, and should not be construed as limiting the technical solutions of the present application.
FIG. 1 is a schematic flow chart of a method for creating a plate of temperature, time and conversion rate for in situ conversion of oil shale according to an embodiment of the present invention;
FIG. 2 is a graph illustrating typical oil shale pyrolysis activation energy distribution versus conversion in accordance with an example of the present invention;
FIG. 3 is a graphical illustration of a typical oil shale in situ conversion temperature-time-conversion relationship according to an example of the present invention;
fig. 4 is a schematic structural diagram of a system for creating a chart of temperature, time and conversion rate for in-situ conversion of oil shale according to an embodiment of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the accompanying drawings and examples, so that how to apply the technical means to solve the technical problems and achieve the corresponding technical effects can be fully understood and implemented. The embodiments and the features of the embodiments can be combined without conflict, and the technical solutions formed are all within the scope of the present invention.
Fig. 1 is a schematic flow chart of a method for creating a chart of temperature, time and conversion rate of in-situ conversion of oil shale according to an embodiment of the present invention, and as shown in the figure, the method includes the following steps:
and S110, selecting an oil shale sample from an oil shale area to be mined, and performing an experiment on the oil shale sample by using a rock pyrolysis analyzer.
And S120, acquiring relation data among pyrolysis activation energy, conversion rate and frequency factor according to the experimental result.
And S130, establishing a relation chart between the reciprocal of the in-situ conversion temperature of the oil shale and the logarithm of the time when the conversion rate is different values based on the relation data.
Specifically, in step S110, a typical oil shale sample in the area to be mined is selected and crushed for standby, and the number of the selected samples and the crushing degree are determined according to the experimental requirements. For example, at least 20g of a sample of oil shale is taken and pulverized into a powder having a particle size of between 0.07mm and 0.15mm for use. In the experiment, 5g of sample is weighed each time, and the experiment result is recorded by using a Rock-Eval 6 type Rock pyrolysis analyzer.
In step S120, the rock pyrolysis analyzer is first used to record the variation data of the pyrolysis yield at different heating rates. For example, hydrocarbon product pyrolysis yield change data was recorded at heating rates of 5, 15, and 25 deg.C/min, respectively. Then, the corresponding relation between the yield of the pyrolysis hydrocarbon and the conversion rate is obtained according to the variation data of the pyrolysis yield. And simulating by using a rock pyrolysis analyzer based on the variation data of the pyrolysis yield to determine the corresponding relation between the pyrolysis activation energy and the pyrolysis hydrocarbon yield. For example, the results of the same heating rate are synthesized into a pyrolysis yield curve using Rock-Eval 6 Rock pyrolysis analyzer kinetic simulation software
And performing simulation, inputting pyrolysis data of 3 different heating rates into kinetic simulation software, and obtaining the relation between the pyrolysis activation energy distribution and the pyrolysis hydrocarbon yield of the oil shale through simulation. And finally, establishing a relationship curve of pyrolysis activation energy and conversion rate according to the relationship between pyrolysis hydrocarbon yield and conversion rate and the relationship between pyrolysis activation energy and pyrolysis hydrocarbon yield.
In addition, when a simulation is performed using a rock pyrolysis analyzer based on variation data of pyrolysis yield to determine a correspondence between pyrolysis activation energy and pyrolysis hydrocarbon yield, a correspondence between pyrolysis activation energy and a frequency factor is also simultaneously determined by the simulation.
Next, in step S130, a linear model of the logarithm of the reciprocal of the temperature and the time for a fixed degree of reaction or for different reactions of the same degree of reaction is established based on the characteristics of the thermal cracking reaction having the first order reaction characteristics.
Specifically, the process of evolving oil shale organic matter (kerogen) to generate oil gas is approximate to a thermal cracking reaction with a first-order reaction characteristic, that is, the reaction speed is in direct proportion to the first power of the reactant concentration, as shown in expression (1):
wherein t is a reaction time in units of s, C is a concentration of a reactant, and k is a reaction rate constant.
The reaction rate dependence of temperature and activation energy is fitted to the arrhenius equation, as shown in expression (2):
k＝k0e-E/RT (2)
in the formula, k0Is a frequency molecule, E is the pyrolysis activation energy, R is the gas constant, and T is the absolute temperature
Integrating expression (1) and substituting expression (2) can give:
in the formula, C0Is the concentration of the reactant at the start of the reaction (t ═ 0), and C is the concentration of the reactant at time t.
Taking logarithm of two sides of expression (3) to obtain:
for a certain fixed degree of reaction, or for different reactions of the same degree of reaction, C is also a constant, and thus expression (4) can be expressed as:
in the formula, A is a constant to be determined, that is, the reciprocal (1/T) of the temperature has a linear relationship with the logarithm (lnt) of the time.
Further, the relational data between the pyrolysis activation energy, the conversion rate and the frequency factor obtained in step S120 is substituted into a linear model as shown in expression (5), to obtain a graph of the relationship between the reciprocal of the temperature (1/T) and the logarithm of the time (lnt) when the conversion rate is different values.
And putting the relation between the reciprocal (1/T) of the temperature and the logarithm (lnt) of the time at different conversion rates into the same coordinate chart, namely establishing the chart of the oil shale in-situ conversion temperature-time-conversion rate.
If the in-situ conversion of the oil shale is predicted and judged at what temperature and at what time, how much conversion rate is achieved, the method can be known only by determining the input points of two factors in a plate.
According to the method for establishing the chart, disclosed by the embodiment of the invention, the dynamic model is obtained by utilizing the oil shale pyrolysis curves under different charts and different heating rates, the distribution of the pyrolysis activation energy (E) of the oil shale and the frequency factor (A) are determined, and the chart of the in-situ conversion temperature-time-conversion rate of the oil shale is established according to the chemical dynamics principle, so that the temperature and the time of the in-situ conversion of the oil shale in a mining area can be rapidly known, and important parameters are provided for engineering decision and cost accounting.
Aiming at the defects of the prior art, the embodiment of the invention provides a method for establishing an oil shale in-situ conversion temperature-time-conversion rate chart according to a chemical kinetics principle in order to effectively predict the temperature and time required under different conversion rates and provide scientific parameters for oil shale in-situ heating conversion mining decisions, and the method can quickly obtain the temperature and time matching relation required under different conversion rates.
The following further illustrates embodiments of the present invention by way of an example.
This example provides a temperature-time-conversion in situ plate creation process for oil shale conversion in the clandelen basin satsuma group.
Weighing 20g of oil shale sample with good lithology homogeneity in the murraya paniculata basin orange pit group, and crushing to obtain the oil shale sample with the particle size of 0.07-0.15 mm.
Each time 5g of sample was weighed, the change in pyrolysis yield at different heating rates (5, 15 and 25 ℃/min) was recorded using a Rock-Eval 6 Rock pyrolysis analyzer, as shown in table 1 for pyrolysis hydrocarbon yield data at a heating rate of 5 ℃/min, and similarly, pyrolysis hydrocarbon yield data at heating rates of 15 and 25 ℃/min were obtained, as shown in table 1:
TABLE 1 pyrolytic Hydrocarbon yield variation (heating rate 5 deg.C/min)
Inputting pyrolysis data of 3 different heating rates, and utilizing Rock-Eval 6 type Rock pyrolysis analyzer dynamics simulation software
The pyrolysis activation energy (E) distribution and frequency factor (a) of the oil shale were obtained as shown in table 2:
TABLE 2 pyrolysis activation energy distribution and frequency factor
The relationship between the hydrocarbon yield and the conversion rate can be known from table 1, the relationship between the hydrocarbon yield and the activation energy can be known from table 2, the corresponding data of the activation energy and the conversion rate can be obtained by taking the hydrocarbon yield as a bridge, and an activation energy and conversion rate curve can be established, as shown in fig. 2.
The process of generating oil gas by the evolution of oil shale organic matter (kerogen) is similar to the thermal cracking reaction with the first-order reaction characteristic,
for a certain fixed degree of reaction, or for different reactions of the same degree of reaction, the reciprocal of the temperature (1/T) and the logarithm of the time (lnt) have a linear relationship as shown in expression (5).
Substituting the conversion rate, the activation energy, the frequency factor data and R (8.3144J/(mol. multidot.K)) in the tables 1 and 2 into the expression (5) to obtain a relational expression of the reciprocal (1/T) of the temperature and the logarithm (lnt) of the time at different conversion rates; for example, the following are the inverse of temperature (1/T) versus log of time (lnt) at 10%, 60%, and 90% conversion, respectively:
the conversion is 10%, the required activation energy E is 238kj/mol, the frequency factor A is 2.565E +16 mol.l-1. s-1, and lnt is 28625/T-37.783.
The conversion rate is 60%, the required activation energy E is 264kj/mol, the frequency factor A is 2.565E +166 mol.l-1. s-1, and lnt is 31752/T-37.783.
The conversion is 90%, the required activation energy E is 280kj/mol, the frequency factor A is 2.565E +166mol · l-1 · s-1, and lnt is 33677/T-37.783.
And putting the relation between the reciprocal (1/T) of the temperature and the logarithm (lnt) of the time at different conversion rates into the same coordinate chart, namely establishing an oil shale in-situ conversion temperature-time-conversion rate chart, as shown in fig. 3, wherein the unit of T is K, and the unit of T is s.
If the in-situ conversion of the oil shale is predicted and judged at what temperature and at what time, how much conversion rate is achieved, only two factors need to be determined to be thrown in the plate (as shown in table 3).
TABLE 3 in situ conversion temperature-time-conversion relationship
For example, from fig. 3 and table 3, it can be seen that if the oil shale in the zone is produced by heating to 350 ℃, the conversion rate of 10% only needs 0.97 hours, the conversion rate of 60% only needs 6 days, and the conversion rate of 90% only needs 4.5 months. If the zone is to be heated to 200 ℃ to recover oil shale, it may be seen as a less practical matter, requiring 240 years to convert even 10% of the oil shale. On the basis of the data parameters, the output and input of the project to be input can be calculated, and reasonable mining temperature is selected, so that important basis is provided for scientific and reasonable decision and economic benefit maximization.
Fig. 4 is a schematic structural diagram of an in-situ oil shale conversion temperature, time and conversion rate chart building system according to an embodiment of the present invention, and as shown in the figure, the system includes:
a sample analysis module 41 which performs the operation of step S110, a data acquisition module 42 which performs the operation of step S120, and a plate creation module 43 which performs the operation of step S130. And will not be described in detail herein.
Although the embodiments of the present invention have been described above, the above descriptions are only for the convenience of understanding the present invention, and are not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A method for establishing a chart of oil shale in-situ conversion temperature, time and conversion rate comprises the following steps:
selecting an oil shale sample from an oil shale area to be mined, and performing an experiment on the oil shale sample by adopting a rock pyrolysis analyzer;
obtaining the relation data among pyrolysis activation energy, conversion rate and frequency factor according to the experimental result;
establishing a relation chart between the reciprocal of the in-situ conversion temperature of the oil shale and the time logarithm when the conversion rate is different values based on the relation data;
the obtaining of the relationship data among the pyrolysis activation energy, the conversion rate and the frequency factor according to the experimental result comprises:
recording the variation data of the pyrolysis yield under different heating rates by using a rock pyrolysis analyzer;
acquiring the corresponding relation between the pyrolysis hydrocarbon yield and the conversion rate according to the variation data of the pyrolysis yield;
performing a simulation with a rock pyrolysis analyzer based on the variation data of the pyrolysis yield to determine a correspondence between pyrolysis activation energy and pyrolysis hydrocarbon yield;
and establishing a relation curve of pyrolysis activation energy and conversion rate according to the corresponding relation between the pyrolysis hydrocarbon yield and the conversion rate and the corresponding relation between the pyrolysis activation energy and the pyrolysis hydrocarbon yield.
2. The method of claim 1, wherein the step of performing a simulation with a rock pyrolysis analyzer based on the pyrolysis yield variation data to determine a correspondence between pyrolysis activation energy and pyrolysis hydrocarbon yield further comprises determining a correspondence between pyrolysis activation energy and a frequency factor.
3. The method of any one of claims 1 to 2, wherein the plotting of the inverse of the in situ conversion temperature of the oil shale against the log of time for different values of conversion based on the relational data comprises:
establishing a linear model of the logarithm of the reciprocal of the temperature and the time for a fixed reaction degree or for different reactions of the same reaction degree according to the characteristics of the thermal cracking reaction with the first-order reaction characteristics;
and substituting the relation data into the linear model to obtain a relation chart between the reciprocal of the temperature and the logarithm of the time when the conversion rate is different values.
4. The method of claim 3, wherein the thermal cracking reaction having the first order reaction characteristic is characterized by the following expression:
wherein E represents the pyrolysis activation energy, T represents the temperature, T represents the time, R is the gas constant, and A is the constant to be determined.
5. The method of claim 1, wherein when performing an experiment on the oil shale sample with a rock pyrolysis analyzer, the method comprises:
crushing the oil shale sample to enable the grain diameter of the oil shale sample to be between 0.07mm and 0.15 mm;
a certain amount of sample is weighed every time, and the measurement data under different heating rates are recorded for multiple times.
6. The method of claim 1, wherein after establishing a chart of the relationship between the inverse of the in situ conversion temperature of the oil shale and the logarithm of the time when the conversion rates are different values, the method further comprises using the chart of the relationship to predict the temperature, the time and the conversion rate of the in situ conversion of the oil shale.
7. A system for creating a chart of temperature, time and conversion rate of in-situ conversion of oil shale comprises:
the sample analysis module is used for selecting an oil shale sample from an oil shale area to be mined and carrying out an experiment on the oil shale sample by adopting a rock pyrolysis analyzer;
the data acquisition module is used for acquiring relationship data among pyrolysis activation energy, conversion rate and frequency factors according to the experimental result;
the obtaining of the relationship data among the pyrolysis activation energy, the conversion rate and the frequency factor according to the experimental result comprises:
recording the variation data of the pyrolysis yield under different heating rates by using a rock pyrolysis analyzer;
acquiring the corresponding relation between the pyrolysis hydrocarbon yield and the conversion rate according to the variation data of the pyrolysis yield;
performing a simulation with a rock pyrolysis analyzer based on the variation data of the pyrolysis yield to determine a correspondence between pyrolysis activation energy and pyrolysis hydrocarbon yield;
establishing a relation curve of pyrolysis activation energy and conversion rate according to the corresponding relation between the pyrolysis hydrocarbon yield and the conversion rate and the corresponding relation between the pyrolysis activation energy and the pyrolysis hydrocarbon yield;
and the chart establishing module is used for establishing a chart of the relation between the reciprocal of the in-situ conversion temperature of the oil shale and the logarithm of the time when the conversion rate is different values based on the relation data.
8. The system of claim 7, wherein the plate creation module creates a plate of the relationship between the reciprocal of the in situ conversion temperature of the oil shale and the logarithm of the time when the conversion is at different values according to the following steps,
establishing a linear model of the logarithm of the reciprocal of the temperature and the time for a fixed reaction degree or for different reactions of the same reaction degree according to the characteristics of the thermal cracking reaction with the first-order reaction characteristics;
and substituting the relation data into the linear model to obtain a relation chart between the reciprocal of the temperature and the logarithm of the time when the conversion rate is different values.
9. The system of claim 8, wherein the thermal cracking reaction having the first order reaction characteristic is characterized by the following expression:
wherein E represents the pyrolysis activation energy, T represents the temperature, T represents the time, R is the gas constant, and A is the constant to be determined.
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| CN112632738B (en) * | 2019-10-09 | 2022-10-04 | 中国石油天然气股份有限公司 | Method and device for determining hydrocarbon generation activation energy in-situ conversion of shale sample |
| CN113756779A (en) * | 2021-08-30 | 2021-12-07 | 陕西省煤田地质集团有限公司 | Method for monitoring and evaluating degree of in-situ pyrolysis reaction of oil-rich coal |
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| CN104849172B (en) * | 2014-02-18 | 2017-08-04 | 中国石油化工股份有限公司 | Oil content of oil shale experimental apparatus for testing and its method of testing |
| CN104007083B (en) * | 2014-06-11 | 2016-09-07 | 中国石油大学(北京) | A kind of oil shale pyrolysis measuring method followed the tracks of based on light |
| CN104156593B (en) * | 2014-08-08 | 2017-04-19 | 中国石油大学(华东) | Shale oil and gas yield evaluation model building and parameter calibrating method applied under closed system |
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