CN115236114A - In-situ exploitation method for oil shale - Google Patents
In-situ exploitation method for oil shale Download PDFInfo
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- 239000004058 oil shale Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 44
- 238000000197 pyrolysis Methods 0.000 claims abstract description 149
- 238000010438 heat treatment Methods 0.000 claims abstract description 104
- 238000002474 experimental method Methods 0.000 claims abstract description 97
- 239000000047 product Substances 0.000 claims description 153
- 238000004364 calculation method Methods 0.000 claims description 100
- 238000006243 chemical reaction Methods 0.000 claims description 98
- 230000004913 activation Effects 0.000 claims description 38
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 6
- 230000010354 integration Effects 0.000 claims description 5
- 238000005065 mining Methods 0.000 abstract description 22
- 239000011435 rock Substances 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 35
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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Abstract
The invention discloses an in-situ mining method of oil shale, which comprises the following steps: obtaining a rock core sample of a target area, and extracting kerogen of the rock core sample; carrying out pyrolysis experiments of preset heating rates on the kerogen to obtain data of the pyrolysis experiments, wherein the data of the pyrolysis experiments comprise the heating rates, the experiment temperatures and the yield of products of the kerogen at the temperatures; obtaining a heating temperature for maximum yield of each product of the kerogen based on data from the pyrolysis experiment and a preconfigured pyrolysis yield model; and obtaining a heating scheme for in-situ exploitation of the oil shale based on the heating temperature and the preset heating rate. The method adopts proper heating temperature and heating rate, thereby improving the yield of the oil shale in the target area, saving energy and improving the yield to the maximum extent and avoiding energy waste.
Description
Technical Field
The invention relates to the technical field of geophysical oil shale mining, in particular to an in-situ mining method for oil shale.
Background
Oil shale is currently the most promising important energy source, and the exploitation modes of oil shale can be divided into ground dry distillation and in-situ exploitation. The ground dry distillation refers to that the oil shale is mined out and is subjected to dry distillation in a dry distillation device on the ground to generate oil shale oil gas. In-situ mining refers to directly heating and dry distilling the oil shale buried underground to convert the oil shale into oil gas and then mining the oil gas in situ without mining the oil shale to the ground. The current ground mining technology has large pollution and high cost, so the research of in-situ heating and exploitation of oil shale is strengthened all over the world, and the in-situ heating mining becomes the main flow direction in the future. Due to the particularity of the oil shale, the oil shale in different areas can be pyrolyzed under different temperature conditions, and products of the oil shale also have various conditions, so that certain difficulties are caused for on-site in-situ exploitation.
By combining the applied hydrocarbon-generating kinetic theory with the modern physical simulation technology, the hydrocarbon-generating patterns of hydrocarbon source rocks in different evolution stages and the geochemical characteristics of products in the research area can be reproduced, the source and the relative quantity of oil gas in the research area can be identified, and the method has important significance for improving the success rate of oil gas exploration in the area and enriching and perfecting the oil gas cause theory. The hydrocarbon generation kinetics theory and research method are rich and various, and are widely applied to hydrocarbon source rock evaluation and basin simulation in oil-gas-containing basins at home and abroad, wherein the most widely applied method is a hydrocarbon generation kinetics method which is mainly used for predicting the hydrocarbon yield under a certain temperature and pressure condition. At present, no relevant research is available on hydrocarbon generation prediction of oil shale in-situ exploitation by applying hydrocarbon generation dynamics.
Kerogen refers to dispersed organic matter in sedimentary oil shale that is insoluble in alkalis, non-oxidizing acids, and non-polar organic solvents. In the prior art, a kerogen sample is subjected to a simulation experiment to obtain activation energy and frequency factors, and is researched by combining with hydrocarbon generation history of other geological data recovery basins, but the research on an oil shale in-situ mining method is not involved.
In addition, the prior art compares four thermodynamic models, namely a DAEM model, a Coats-Redfern method, a FWO method and a Doyle method, and the DAEM model is preferably used as an oil shale pyrolysis kinetic analysis model. But was not verified by actual physical simulation experiments and was not used to guide actual production.
In addition, the prior art also obtains thermal fracture factor parameters of oil shale, which include: oil shale physical parameters and/or dry distillation environment parameters which influence the occurrence of thermal cracking of the oil shale in the dry distillation process; obtaining a corresponding thermal cracking factor index according to the thermal cracking factor parameter of the oil shale, wherein the thermal cracking factor index is the ratio of the thermal cracking factor parameter to a corresponding preset factor calibration value and/or the ratio of the preset factor calibration value to the thermal cracking factor parameter; and obtaining the probability of the oil shale thermal fracture according to the numerical value of the product of the indexes of the plurality of thermal fracture factors of the oil shale.
In the prior art, the severe reaction section of oil shale pyrolysis is mainly concentrated in the medium temperature section of 350-550 ℃, an oil shale pyrolysis reaction kinetic model is established according to propyne test data, the Gixasal oil shale pyrolysis belongs to the first-order reaction, and the kinetic parameters related to the activation energy and the frequency factor are calculated by using a mapping method.
In view of the above, there is a need for an in situ heating mining method that can improve oil shale yield and save energy.
Disclosure of Invention
The invention provides an in-situ mining method for oil shale, which solves the technical problems that the yield of the in-situ mining of the oil shale is not high and the energy is wasted in the prior art, thereby improving the yield of the oil shale and saving the energy.
A method for in-situ exploitation of oil shale comprises the following steps:
obtaining a rock core sample of a target area, and extracting kerogen of the rock core sample;
carrying out pyrolysis experiments of preset heating rates on the kerogen to obtain data of the pyrolysis experiments, wherein the data of the pyrolysis experiments comprise the heating rates, the experiment temperatures and the yield of products of the kerogen at the temperatures;
obtaining a heating temperature for maximum yield of each product of the kerogen based on data from the pyrolysis experiment and a preconfigured pyrolysis yield model;
and obtaining a heating scheme for in-situ exploitation of the oil shale based on the heating temperature and the preset heating rate.
In an embodiment of the present invention, it is,
the step of obtaining a heating temperature for maximum yield of each product of kerogen based on the pyrolysis experimental data and a preconfigured pyrolysis yield model comprises the steps of:
obtaining activation energy and frequency factors of each product of the kerogen based on data of the pyrolysis experiment through an Arrhenius calculation formula;
constructing the pyrolysis yield model;
and obtaining the heating temperature corresponding to the maximum yield of each product of the kerogen based on the data of the pyrolysis experiment and the pyrolysis yield model.
In an embodiment of the present invention, it is,
the step of obtaining the activation energy and frequency factor of each product of kerogen by an arrhenius calculation formula based on the data of the pyrolysis experiment comprises the steps of:
obtaining the activation energy of each product of the kerogen based on the data of the pyrolysis experiment through an Arrhenius integration calculation formula;
obtaining frequency factors of each product of the kerogen by an arrhenius index calculation formula based on data of the pyrolysis experiment and the activation energy.
In an embodiment of the present invention in which,
the step of constructing the pyrolysis yield model comprises:
obtaining a first integral calculation formula of the volume of each product with respect to the experimental temperature based on a kinetic equation calculation formula of solid pyrolysis, a parallel first-order reaction calculation formula, the arrhenius index calculation formula and the temperature rise rate condition calculation formula;
dividing the reaction of the product into N reactions which occur in parallel, and obtaining a second integral calculation formula of the volume ratio of each product of the single reaction relative to the experimental temperature based on the first integral calculation formula after arrangement;
integrating and finishing the second integral calculation formula to obtain a calculation formula of the yield of all reactions of each product at each experimental temperature;
a calculation of a pyrolysis yield model for each of the products is obtained based on the yield calculations.
In an embodiment of the present invention in which,
the calculation for the pyrolysis yield model is:
wherein X is the total yield of a certain product of N parallel reactions;
xj is the yield of a single reaction product;
Xj 0 is an initial temperature T 0 The yield of the next product;
T 0 is the initial temperature in K;
t is the highest reaction temperature corresponding to the total yield, and the unit is K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
j is a single reaction and N is the number of single reactions;
in an embodiment of the present invention, it is,
the first integral calculation formula is:
wherein V is the volume of a product at temperature T;
t is the reaction temperature in K;
a is a pre-exponential factor or a frequency factor;
e is the base of the natural logarithm;
e is the experimental activation energy, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
V ∞ the volume of a certain product at the temperature T when the reaction time is infinite,
in an embodiment of the present invention, it is,
the second integral calculation formula is:
wherein x is i (T) is the volume ratio of the single reaction product at the temperature T;
t is the reaction temperature and has the unit of K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
x ∞ (j) Is the volume ratio of the product of a single reaction at the temperature T when the reaction time is infinite;
j is a single reaction.
In an embodiment of the present invention, it is,
the yield calculation formula is:
wherein X (T) is the sum of the volume ratios of the single reaction products at the respective temperatures;
t is the reaction temperature in K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
x ∞ (j) Is the volume ratio of the product of a single reaction at the temperature T when the reaction time is infinite;
j is a single reaction.
In an embodiment of the present invention, it is,
the step of obtaining the heating temperature corresponding to the maximum yield of each product of the kerogen based on the data of the pyrolysis experiment and the pyrolysis yield model comprises the following steps:
fitting to obtain a maximum yield of each product of the kerogen based on the data of the pyrolysis experiment;
adding the yield of each product of the kerogen at each of the experimental temperatures and the maximum yield to obtain an overall yield of each product of the kerogen;
and sequentially substituting the frequency factor, the activation energy, the initial experimental temperature, the yield at the initial experimental temperature, the heating rate and the total yield corresponding to each product of the kerogen into a calculation formula of the pyrolysis yield model, and solving to obtain the heating temperature corresponding to the maximum yield of each product of the kerogen.
In an embodiment of the present invention, it is,
the ramp rates include 20 ℃/h and 2 ℃/h.
One or more embodiments of the present invention may have the following advantages over the prior art:
the invention provides an in-situ mining method for oil shale, which obtains the maximum yield of each product of kerogen through fitting of a pyrolysis simulation experiment, and obtains the optimal heating scheme for oil shale mining through a pre-constructed pyrolysis model, thereby improving the yield of oil shale heating mining and saving energy.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the 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, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic flow diagram of an in situ mining method of example 1 of the present invention;
FIG. 2 is a schematic illustration of a process for predicting in situ hydrocarbon production in accordance with example 1 of the present invention;
FIG. 3 is a schematic view of a process for obtaining pyrolysis parameters of oil shale in example 2 of the present invention;
FIG. 4 is a graph showing the yield of methane experimental data fitted in example 3 of the present invention;
FIG. 5 is a graph showing the yield of the C2-C5 experimental data in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the following detailed description of the present invention with reference to the accompanying drawings is provided to fully understand and implement the technical effects of the present invention by solving the technical problems through technical means. It should be noted that, as long as there is no conflict, the embodiments and the features of the embodiments of the present invention may be combined with each other, and the technical solutions formed are within the scope of the present invention.
First embodiment
FIG. 1 is a schematic flow chart of the in-situ mining method of the present embodiment;
FIG. 2 is a schematic diagram of the in situ hydrocarbon production prediction flow of the present embodiment.
A method for in-situ exploitation of oil shale comprises the following steps:
obtaining a core sample of a target area, and extracting kerogen of the core sample;
carrying out pyrolysis experiment of a preset heating rate on kerogen to obtain data of the pyrolysis experiment;
obtaining a heating temperature for maximum yield of each product of the kerogen based on data from the pyrolysis experiment and a preconfigured pyrolysis yield model;
and obtaining a heating scheme for in-situ exploitation of the oil shale based on the heating temperature and the preset heating rate.
Specifically, in this embodiment, a method for in-situ mining of oil shale includes the following steps:
s100, obtaining a core sample of the target area, and extracting kerogen of the core sample.
Obtaining a plurality of core samples in the well logging of a target area, and extracting a plurality of kerogen from the core samples, wherein the kerogen accounts for at least12 parts of methane CH, 2 parts of methane CH being used in S0 products C1-C7 4 Yield pyrolysis experiment, 2 parts of yield pyrolysis experiment for S0 products C2-C5, 2 parts of yield pyrolysis experiment for S1 liquid hydrocarbon products C8-C32, 2 parts of yield pyrolysis experiment for S2 cracking hydrocarbon products, 2 parts of yield pyrolysis experiment for S3 carbon dioxide products, and 2 parts of content pyrolysis experiment for TOC organic matter products, wherein the extraction of kerogen of a plurality of rock core samples is beneficial to obtaining parameters of various pyrolysis experiments.
And S110, carrying out a pyrolysis experiment of a preset heating rate on the kerogen to obtain data of the pyrolysis experiment.
Specifically, in this embodiment, a physical pyrolysis simulation experiment with 2 temperature rise rates is performed on 12 parts of kerogen for each product, where the temperature rise rates include 20 ℃/h and 2 ℃/h, after a pyrolysis test is performed on 12 parts of kerogen, data of the pyrolysis test is obtained, and the data of the pyrolysis test includes each temperature rise rate, each test temperature, and a yield of each product of kerogen at each temperature, and each data of the pyrolysis test can be accurately obtained by performing a plurality of pyrolysis tests on kerogen.
And S120, obtaining the heating temperature of the maximum yield of each product of the kerogen based on the data of the pyrolysis experiment and a preconfigured pyrolysis yield model.
Specifically, the heating temperature for obtaining the maximum yield of each product of the kerogen based on each heating rate, each experimental temperature, the yield of each product of the kerogen at each temperature in the pyrolysis experimental data and a pre-constructed pyrolysis yield model comprises the following steps:
1) Obtaining the activation energy and frequency factor of each product of the kerogen by an Arrhenius calculation formula based on the data of the pyrolysis experiment;
2) Constructing a pyrolysis yield model;
3) And obtaining the heating temperature corresponding to the maximum yield of each product of the kerogen based on the data of the pyrolysis experiment and the pyrolysis yield model.
Further, in this example, the activation energy and frequency factor of each product of kerogen were obtained by the arrhenius calculation formula based on the data of the pyrolysis experiment, including the following steps:
(1) obtaining the activation energy of each product of the kerogen by an Arrhenius integration calculation formula based on the data of the pyrolysis experiment;
specifically, the reaction rate constants k at the experimental temperatures T1 and T2 were obtained based on different experimental temperatures and reaction conditions in the data of the kerogen pyrolysis experiment 1 And k 2 Then the experimental temperature T is measured 1 And T 2 And the constant R number of the mol gas is brought into an Arrhenius integration calculation formula, and the activation energy of each product of the kerogen can be obtained by solving.
The Arrhenius integral calculation formula is as follows:
wherein: k is a radical of 1 And k 2 Respectively the experimental temperature T 1 And T 2 The reaction rate constant of time;
a is a pre-exponential factor or a frequency factor;
ea is the experimental activation energy, and the unit is kcal/mol;
T 1 and T 2 Is the experimental temperature in K;
r is a molar gas constant of 1.98910, in kcal/mol.
(2) The frequency factors for each product of kerogen were obtained by an arrhenius index calculation based on the data from the pyrolysis experiments and the activation energy.
Specifically, the solution can be obtained based on the fact that each experiment temperature T, the reaction rate constant k of each experiment temperature, the activation energy E of each product, and the molar gas constant R in the data of the kerogen pyrolysis experiment are substituted into an arrhenius index calculation formula.
The calculation formula of the arrhenius index is as follows:
wherein k is a reaction rate constant at a temperature T;
a is a pre-exponential factor or a frequency factor;
e is the base of the natural logarithm;
e is the experimental activation energy, and the unit is kcal/mol;
t is the experimental temperature in K;
r is a molar gas constant of 1.98910, in kcal/mol.
Further, in this embodiment, the step of constructing the pyrolysis yield model includes:
(1) obtaining a first integral calculation formula of the volume of each product with respect to the experimental temperature based on a kinetic equation calculation formula of solid pyrolysis, a parallel first-order reaction calculation formula, an Arrhenius index calculation formula and a heating rate condition calculation formula;
(2) dividing the reaction of the product into N reactions which occur in parallel, and obtaining a second integral calculation formula of the volume ratio of each product of the single reaction with respect to the experimental temperature after the first integral calculation formula is based on and arranged;
(3) integrating and finishing the product according to a second integral calculation formula to obtain a calculation formula of the yield of all the reactions of each product at each experimental temperature;
(4) calculations for a model of pyrolysis yield for each product were obtained based on the yield calculations.
Further, based on the kinetic equation calculation formula of solid pyrolysis, the parallel first-order reaction calculation formula, the arrhenius index calculation formula and the temperature rise rate condition calculation formula, the process of obtaining the first integral calculation formula of the volume of each product with respect to the experimental temperature is as follows:
the kinetic equation calculation for solid pyrolysis was obtained as:
wherein V is the volume of the product;
t is the reaction time;
k is a reaction rate constant at temperature T;
f (V) is a function of the volume of the product as a function of V.
The parallel first-order reaction calculation formula was obtained as:
f(V)＝V ∞ -V
wherein f (V) is a volume function of a product as a function of V;
V ∞ volume of a product at infinite reaction time;
v is the volume of one product at a time.
And obtaining a temperature rise rate condition calculation formula:
wherein V is the volume of the product; t is the reaction time;
Based on the kinetic equation calculation formula of solid pyrolysis, the parallel first-stage reaction calculation formula, the arrhenius index calculation formula and the heating rate condition calculation formula, the f (V) expression in the parallel first-stage reaction calculation formula is substituted into the kinetic equation calculation formula, the k expression in the arrhenius index calculation formula is substituted into the kinetic equation calculation formula, and the heating rate condition calculation formula is substituted
And (4) in the expression kinetic equation calculation formula, finishing to obtain a first integral calculation formula of the volume of each product relative to the experimental temperature.
In this embodiment, the first integral calculation formula is:
wherein V is the volume of a certain product at temperature T;
t is the reaction temperature in K;
a is a pre-exponential factor or a frequency factor;
e is the base of the natural logarithm;
e is the experimental activation energy, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
V ∞ the volume of a certain product at temperature T at which the reaction time is infinite.
Further, the procedure of dividing the reaction of the product into N reactions occurring in parallel, based on the first integral calculation formula, and obtaining the second integral calculation formula of the volume ratio of each product of the single reaction with respect to the experimental temperature after the work-up is as follows:
first, the reaction of this product is divided into N reactions taking place in parallel, based on the above-mentioned one first integral calculation relating product volume V to temperature T, obtaining a calculation relating product volume Vj to temperature T for a single reaction:
wherein Vj is the volume of the product of a single reaction;
t is the experimental temperature in K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
V ∞ (j) Is reaction time ofVolume of product of a single reaction at infinity;
j is a single reaction.
Then, let
Substituting the product volume Vj and the temperature T related calculation formula of the single reaction, and finishing to obtain a second integral calculation formula of the single reaction volume ratio and the temperature T.
In this embodiment, the second integral calculation formula is:
wherein x is i (T) is the volume ratio of the single reaction product at the temperature T;
t is the reaction temperature in K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
x ∞ (j) Is the volume ratio of the product of a single reaction at the temperature T when the reaction time is infinite;
j is a single reaction.
Further, the calculation of the yield of all the reactions of each product at each experimental temperature after integration and working up based on the second integral calculation formula is as follows:
due to the fact that
The second integral calculation is integrated and then arranged to obtain a calculation formula of the yield of all reactions of each product at each experimental temperature.
In this example, the yield is calculated as:
wherein X (T) is the sum of the volume ratios of the single reaction products at the temperatures;
t is the reaction temperature in K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
x ∞ (j) Is the volume ratio of the product of a single reaction at the temperature T when the reaction time is infinite;
j is a single reaction.
Further, the calculation formula of the pyrolysis yield model of each product was obtained by performing accumulation arrangement based on the above yield calculation formula.
In this example, the calculation for the pyrolysis yield model is:
wherein X is the total yield of a certain product of N parallel reactions;
xj is the yield of a single reaction product;
Xj 0 is an initial temperature T 0 The yield of the next product;
T 0 to the initial temperature, singlyThe bit is K;
t is the highest reaction temperature corresponding to the total yield, and the unit is K;
aj is a pre-exponential factor or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
j is a single reaction, and N is the number of single reactions;
further, in this embodiment, the step of obtaining the heating temperature corresponding to the maximum yield of each product of kerogen based on the data of the pyrolysis experiment and the pyrolysis yield model comprises:
(1) fitting based on the data of the pyrolysis experiment to obtain the maximum yield of each product of the kerogen;
specifically, the procedure of obtaining the maximum yield of each product of kerogen based on fitting of the data of the pyrolysis experiment was as follows:
through the pyrolysis experiment carried out on the multi-component kerogen, each temperature rise rate (such as 20 ℃/h and 2 ℃/h), each experiment temperature and each yield of the kerogen product at each temperature in the pyrolysis experiment are obtained.
The initial temperature of the experimental temperature is set to be the minimum temperature required by the target area, for example, 200 ℃ or 300 ℃ is selected, 2 parts of kerogen are subjected to a pyrolysis experiment according to the heating rate of 20 ℃/h and 2 ℃/h, the yield of each product corresponding to the experimental temperature is obtained after every 1 time of heating, and the yield of each product corresponding to each experimental temperature is obtained until the temperature is increased to the preset experimental temperature and the product can not be obtained. The heating rate can be adjusted adaptively according to various characteristics of kerogen, and is not limited to these 2 heating rates. And fitting the yield corresponding to each experiment and a certain product obtained by the 2 kinds of heating rate pyrolysis experiments in a rectangular coordinate system to obtain a fitting curve related to the yield and the temperature of the pyrolysis experiment of the certain product. By the same method, fitted curves of pyrolysis experimental yield and temperature correlation of various products are obtained. And obtaining the maximum upper limit experimental yield of each product through the coordinate corresponding relation corresponding to the highest point of the fitted curve and the yield. In this example, this maximum upper experimental yield is defined as the maximum yield of each product.
(2) Adding the yield and the maximum yield of each product of the kerogen at each experimental temperature to obtain the total yield of each product of the kerogen;
specifically, the process of adding the yield and maximum yield of each product of kerogen at each experimental temperature to obtain the total yield of each product of kerogen is as follows:
the total yield of each product in kerogen was obtained by adding all the products of the same type starting from the initial experimental temperature up to the highest experimental temperature at which the pyrolysis experiment was stopped.
(3) And sequentially substituting the frequency factor, the activation energy, the initial experiment temperature, the yield at the initial experiment temperature, the heating rate and the total yield corresponding to each product of the kerogen into a calculation formula of a pyrolysis yield model, and solving to obtain the heating temperature corresponding to the maximum yield of each product of the kerogen.
Specifically, the frequency factor, the activation energy, the initial experiment temperature, the yield at the initial experiment temperature, the heating rate and the total yield corresponding to a certain product of the kerogen are sequentially introduced into a calculation formula of a pyrolysis yield model, the heating temperature corresponding to the maximum yield of the certain product of the kerogen is obtained through solving, and the heating temperature corresponding to the maximum yield of all the products is sequentially obtained according to the same method.
S130, obtaining a heating scheme for in-situ exploitation of the oil shale based on the heating temperature and the preset heating rate.
Specifically, the heating temperature corresponding to the fitted maximum yield is obtained according to the pyrolysis yield model of each product, and then the heating rate and the initial temperature suitable for the in-situ exploitation of the oil shale in the target area are selected according to each heating rate of the experiment, so that the heating scheme for the in-situ exploitation of the oil shale is obtained.
Further, a heating scheme for in-situ exploitation of the oil shale is obtained based on the heating temperature and the preset heating rate, a pyrolysis experiment of the preset heating rate is performed on the core sample, data of the pyrolysis experiment of the core sample is obtained, and the heating scheme for in-situ exploitation of the oil shale based on the kerogen pyrolysis experiment and the data of the core sample pyrolysis experiment can be perfected.
Due to the chemical reactions that occur in geological processes and under laboratory controlled conditions, have the same chemical kinetic properties, i.e. the same hydrocarbon generation kinetic parameters. Therefore, in the embodiment, a hydrocarbon generation kinetic method is adopted, and a chemical kinetic theory is combined to obtain each kinetic parameter, a bridge between a laboratory and geological application is built, and then a low-temperature long-time slow reaction process under a geological condition is fitted, so that a pyrolysis yield model of the total product yield and the heating temperature is built.
In order to reasonably conduct core heating exploitation and product collection, the embodiment conducts a pyrolysis experiment on a formation core sample and extracted kerogen in advance to obtain dynamic data of a product, and constructs a pyrolysis yield model of a total product yield and a heating temperature by combining calculation formulas such as a parallel first-order reaction, and the like, so that a heating scheme for oil shale in-situ exploitation and a final predicted hydrocarbon generation condition of a target area are obtained, energy can be saved to the greatest extent, the yield is improved, and energy waste is avoided.
According to the method of the embodiment, the oil and gas yield changing along with time can be obtained, and the whole exploitation production process can be known conveniently on site in real time. According to the method, a data support and analysis means can be provided for the in-situ exploitation of the oil shale heated by the fluid in the field of the target area, and the exploitation efficiency of the oil shale is improved.
In this embodiment, the data of the relevant parameters can also be obtained through the pyrolysis experiment, and other parameters at each temperature except for the total yield in the pyrolysis yield model are obtained, and then the parameters are substituted into the calculation formula of the pyrolysis yield model, so that the predicted hydrocarbon generation condition of the target area corresponding to each experimental temperature can be obtained, as shown in fig. 2.
In summary, this embodiment provides a method for in-situ mining of oil shale, which includes obtaining a total product yield by fitting through pyrolysis experimental data of kerogen of a core sample to obtain a maximum yield, constructing a pyrolysis yield model of the total product yield and a heating temperature, and obtaining the heating temperature of the maximum yield of in-situ mining of oil shale in a target area, so as to obtain a heating scheme for in-situ mining of oil shale and a final predicted hydrocarbon generation condition of the target area. The embodiment adopts the appropriate heating temperature and heating rate, so that the yield of the oil shale in the target area is improved, the energy is saved to the maximum extent, the yield is improved, and the energy waste is avoided.
Second embodiment
Fig. 3 is a schematic flow chart of obtaining pyrolysis parameters of oil shale according to the embodiment;
the embodiment provides an in-situ exploitation method of oil shale, which comprises the following steps:
obtaining a core sample of a target area, and extracting kerogen of the core sample;
carrying out pyrolysis experiments of a preset heating rate on kerogen and core samples to obtain data of the pyrolysis experiments;
obtaining heating temperatures for maximum yields of each product of the kerogen and core samples based on data from the pyrolysis experiment and a preconfigured pyrolysis yield model;
and obtaining a heating scheme for in-situ exploitation of the oil shale based on the heating temperature and the preset heating rate.
Further, in this embodiment, a pyrolysis experiment with a preset temperature rise rate is performed on the kerogen and core samples, and obtaining data of the pyrolysis experiment includes the following steps:
firstly, taking out sample tubes of kerogen and core samples which are heated at high temperature, putting the sample tubes into a vacuum system, and releasing gas into the vacuum system;
then, connecting the vacuum system with a gas chromatograph on line, and adopting a vacuum sampling loop to sample, wherein the analysis of C1-C5 hydrocarbon gas and CO, CO2, H2, N2 and O2 can be completed by sampling each time;
secondly, after the gas analysis is finished, freezing an online sample bottle by using liquid nitrogen to collect a small amount of C6-10 light hydrocarbon diffused into the vacuum glass tube;
thirdly, after the sample bottle is taken down, injecting a dichloromethane solvent, taking the gold tube out of the high-pressure kettle, shearing the gold tube together with the sample, putting the gold tube into the sample bottle, and vibrating by ultrasonic to completely dissolve oil generated in the gold tube into the solvent; thus effectively avoiding the loss of C6-C10 hydrocarbons;
thirdly, taking 1ml of supernatant liquor in a 4ml sample bottle, transferring the supernatant liquor into a 2ml sample bottle, performing chromatographic analysis by using an automatic sample injector, and performing light hydrocarbon (C6-C14) quantitative analysis by using deuterated C24 as an internal standard;
and finally, obtaining data of each pyrolysis experiment, including each heating rate (such as 20 ℃/h and 2 ℃/h), each experiment temperature, the yield of each product of kerogen at each temperature, and the yield of each product of the core sample at each temperature according to the data obtained in the steps and the pressure control system, the temperature control system and the data processing system.
And then, the rest steps and contents in the first embodiment are adopted to obtain the heating scheme for in-situ exploitation of the oil shale, so that the in-situ heating exploitation of the oil shale is carried out in the target area.
This example allows for more accurate pyrolytic experimental data for kerogen and core samples.
Third embodiment
FIG. 4 is a graph showing the yield of the experimental methane data;
FIG. 5 is a graph showing the yield of the C2-C5 experimental data fit in this example;
the embodiment of the method for in-situ exploitation of oil shale is specifically described in this embodiment, and includes the following steps:
obtaining a rock core sample of a target area, and extracting kerogen of the rock core sample;
carrying out pyrolysis experiment of a preset heating rate on kerogen to obtain data of the pyrolysis experiment;
obtaining a heating temperature for maximum yield of each product of the kerogen based on data from the pyrolysis experiment and a preconfigured pyrolysis yield model;
and obtaining a heating scheme for in-situ exploitation of the oil shale based on the heating temperature and the preset heating rate.
Specifically, the weight of the extracted kerogen was 7.44mg, the temperature rise rate was set to 20 ℃/h and 2 ℃/h, and the pyrolysis experiment of the kerogen resulted in the yield of methane CH4 in the S0 products C1-C7, the yield of the S1 liquid hydrocarbon products C8-C32, the yield of the S2 cracked hydrocarbon products, the yield of the S3 carbon dioxide products, and the TOC organic matter product content, wherein the yield of S1 was 3.36ml/g, the yield of S2 was 156.3ml/g, the yield of S3 was 2.05ml/g, and the TOC content was 55.41%, and the experimental temperature and the experimental yield of the kerogen products at each temperature were recorded.
According to the process of constructing the pyrolysis yield model in embodiment 1, the activation energy and the frequency factor of methane are obtained, and then according to each experimental temperature in the pyrolysis experimental data and the experimental yield of methane obtained at the corresponding temperature, the experimental data points are fitted in a rectangular coordinate system with the abscissa as the experimental temperature and the ordinate as the methane yield, so as to obtain a fitting curve related to the pyrolysis experimental yield of methane and the temperature, as shown in fig. 4.
The maximum upper limit experimental yield of the methane of 180ml/g is obtained through the coordinate corresponding relation corresponding to the highest point of the fitted curve and the yield. In this example, this maximum upper experimental yield of 180ml/g is defined as the maximum yield of methane.
The total yield of methane in kerogen was then obtained by adding all of the same type of products starting at an initial experimental temperature of 300 c up to a maximum experimental temperature of 650 c at which the pyrolysis experiment was stopped.
And then sequentially bringing the frequency factor, the activation energy, the initial experiment temperature, the yield at the initial experiment temperature, the heating rate and the total yield corresponding to the methane of the kerogen into a calculation formula of a pyrolysis yield model, and solving the heating temperature corresponding to the maximum yield of the methane of the kerogen.
Data were calculated in part and friedman type analysis with response score = x is shown in table 1:
TABLE 1 heating analysis calculation data sheet
Approximate A and E values for the x interval from 0 to 1 were calculated, see Table 2:
tables 2A and E data sheet
| x | A(s -1 ) | E(cal/mol) |
| 0.1 | 2.7887×10 13 | 54897 |
| 0.2 | 1.1203×10 15 | 62535 |
| 0.3 | 1.7247×10 14 | 61720 |
| 0.4 | 7.5906×10 12 | 58723 |
| 0.5 | 2.8156×10 12 | 58590 |
| 0.6 | 5.7451×10 11 | 57677 |
| 0.7 | 1.3524×10 11 | 57089 |
| 0.8 | 2.6803×10 10 | 56518 |
| 0.9 | 2.6220×10 11 | 62811 |
Calculated as a =2.7012 × 10 12 s -1 ，E＝58698cal/mol。
Wherein, when the heating speed is 20 ℃/h, the temperature of 50 percent of methane yield is 518.91 ℃; the temperature for 50% methane yield was 474.88 ℃ at a heating rate of 2 ℃/h.
In the same way, a fitted curve relating yield to pyrolysis experiment and temperature of C2-C5 products was obtained, as shown in fig. 5. The maximum upper experimental yield of the C2-C5 products was obtained to be 33ml/g by the coordinate correspondence to the highest point of the fitted curve and the yield. In this example, this maximum upper experimental yield of 33ml/g is defined as the maximum yield of methane.
The kerogen C2-C5 products were then added from the initial experimental temperature of 300 ℃ up to the maximum experimental temperature of 650 ℃ at which the pyrolysis experiment was stopped, to obtain the total yield of C2-C5 products in kerogen.
And then sequentially bringing the frequency factor, the activation energy, the initial experiment temperature, the yield at the initial experiment temperature, the heating rate and the total yield corresponding to the C2-C5 product of the kerogen into a calculation formula of a pyrolysis yield model, and solving the heating temperature corresponding to the maximum yield of the C2-C5 product of the kerogen.
Partly calculated data, friedman type analysis with reaction score = x is shown in table 3:
TABLE 3 heating analysis calculation data sheet
Approximate A and E values for the x interval from 0 to 1 were calculated, see Table 4:
TABLE 4A, E data sheet
| x | A(s -1 ) | E(cal/mol) |
| 0.1 | 6.8224×10 12 | 49984 |
| 0.2 | 7.8112×10 13 | 54949 |
| 0.3 | 3.3390×10 13 | 55123 |
| 0.4 | 7.7982×10 13 | 57457 |
| 0.5 | 1.8973×10 13 | 56615 |
| 0.6 | 2.2207×10 13 | 57909 |
| 0.7 | 4.2022×10 13 | 59992 |
| 0.8 | 3.4395×10 14 | 64468 |
| 0.9 | 1.0013×10 13 | 61460 |
A =1.8542 × 1013s-1, E =56728cal/mol is calculated.
Wherein the temperature at which 50% of the C2-C5 product yield is 457.24 ℃ when the heating rate is 20 ℃/h; heating rate of 2 ℃/h, 50% C2-C5 product yield temperature of 418.32 ℃.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is 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 (10)
1. A method for in-situ exploitation of oil shale, comprising the steps of:
obtaining a core sample of a target area, and extracting kerogen of the core sample;
carrying out pyrolysis experiments of preset heating rates on the kerogen to obtain data of the pyrolysis experiments, wherein the data of the pyrolysis experiments comprise the heating rates, the experiment temperatures and the yield of products of the kerogen at the temperatures;
obtaining a heating temperature for maximum yield of each product of the kerogen based on data from the pyrolysis experiment and a preconfigured pyrolysis yield model;
and obtaining a heating scheme for in-situ exploitation of the oil shale based on the heating temperature and the preset heating rate.
2. The method of claim 1, wherein said step of obtaining a heating temperature for maximum yield of each product of kerogen based on said pyrolysis experimental data and a preconfigured pyrolysis yield model comprises the steps of:
obtaining activation energy and frequency factor of each product of the kerogen based on the data of the pyrolysis experiment through an Arrhenius calculation formula;
constructing the pyrolysis yield model;
and obtaining the heating temperature corresponding to the maximum yield of each product of the kerogen based on the data of the pyrolysis experiment and the pyrolysis yield model.
3. The method of claim 2, wherein said step of obtaining said activation energy and frequency factors for each product of kerogen by an arrhenius calculation based on said data from said pyrolysis experiment comprises the steps of:
obtaining the activation energy of each product of the kerogen based on the data of the pyrolysis experiment through an Arrhenius integration calculation formula;
obtaining frequency factors of each product of the kerogen by an arrhenius index calculation formula based on data of the pyrolysis experiment and the activation energy.
4. The method of claim 2, wherein the step of constructing the pyrolysis yield model comprises:
obtaining a first integral calculation formula of the volume of each product with respect to the experimental temperature based on a kinetic equation calculation formula of solid pyrolysis, a parallel first-order reaction calculation formula, the arrhenius index calculation formula and the temperature rise rate condition calculation formula;
dividing the reaction of the products into N reactions which occur in parallel, and obtaining a second integral calculation formula of the volume ratio of each product of the single reaction relative to the experimental temperature based on the first integral calculation formula after arrangement;
integrating and finishing the second integral calculation formula to obtain a yield calculation formula of all reactions of each product at each experimental temperature;
a calculation of a pyrolysis yield model for each of the products is obtained based on the yield calculations.
5. The method of claim 4,
the calculation for the pyrolysis yield model is:
wherein X is the total yield of a certain product of N parallel reactions;
xj is the yield of a single reaction product;
Xj 0 at an initial temperature T 0 The yield of the product;
T 0 is the initial temperature in K;
t is the highest reaction temperature corresponding to the total yield, and the unit is K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
j is a single reaction and N is the number of single reactions.
6. The method of claim 4,
the first integral calculation formula is:
wherein V is the volume of a certain product at temperature T;
t is the reaction temperature in K;
a is a pre-exponential factor or a frequency factor;
e is the base of the natural logarithm;
e is the experimental activation energy, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
V ∞ is the volume of a certain product at temperature T at which the reaction time is infinite.
7. The method of claim 4,
the second integral calculation formula is:
wherein x is i (T) is the volume ratio of the single reaction product at the temperature T;
t is the reaction temperature in K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
x ∞ (j) Is the volume ratio of the product of a single reaction at the temperature T when the reaction time is infinite;
j is a single reaction.
8. The method of claim 4,
the calculated yield is:
wherein X (T) is the sum of the volume ratios of the single reaction products at the respective temperatures;
t is the reaction temperature in K;
aj is a pre-exponential or frequency factor of a single reaction;
e is the base of the natural logarithm;
ej is the experimental activation energy of a single reaction, and the unit is kcal/mol;
r is a molar gas constant of 1.98910, in kcal/mol;
x ∞ (j) Is the volume ratio of the product of a single reaction at the temperature T when the reaction time is infinite;
j is a single reaction.
9. The method of claim 2, wherein the step of obtaining a heating temperature corresponding to a maximum yield of each product of the kerogen based on the data from the pyrolysis experiment and the pyrolysis yield model comprises:
fitting to obtain a maximum yield of each product of the kerogen based on the data of the pyrolysis experiment;
adding the yield of each product of the kerogen at each of the experimental temperatures and the maximum yield to obtain an overall yield of each product of the kerogen;
and sequentially substituting the frequency factor, the activation energy, the initial experimental temperature, the yield at the initial experimental temperature, the heating rate and the total yield corresponding to each product of the kerogen into a calculation formula of the pyrolysis yield model, and solving to obtain the heating temperature corresponding to the maximum yield of each product of the kerogen.
10. The method according to any one of claims 1 to 9,
the ramp rates included 20 ℃/h and 2 ℃/h.
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