阅读说明：本技术 一种泥页岩馏分含油量及其分子组成同步分析方法 (Synchronous analysis method for oil content and molecular composition of shale fraction ) 是由 张居和 冯子辉 曾花森 霍秋立 鄢仁勤 张博为 姜革 冯军 于 2020-05-30 设计创作，主要内容包括：本发明公开了一种泥页岩馏分含油量及其分子组成同步分析方法,利用泥页岩含油量与精细组分同步实验分析装置,采用30℃～90℃、90℃～150℃、100℃～200℃、150℃～250℃、250℃～300℃5个温度段、每个温度段升温速率均为25℃/min、终温均恒温5min,将页岩含油量切割成5个主要馏分气、汽油、煤油、柴油和重质油,进行泥页岩油馏分含油量及其分子组成同步检测、外标法定量,利用馏分含油量、馏分分子组成、轻重比等分析参数指标,对泥页岩含油性和流动性及性质评价,达到对泥页岩油储层评价和流动性预测的目的,满足泥页岩油勘探对地质实验技术的需求。为泥页岩油“四性”评价、“甜点”优选等勘探生产提供了重要地质实验依据。(The invention discloses a shale oil content and molecular composition synchronous analysis method, which comprises the steps of utilizing a shale oil content and fine component synchronous experimental analysis device, cutting shale oil content into 5 main fraction gases, gasoline, kerosene, diesel oil and heavy oil by adopting 5 temperature sections of 30-90 ℃, 90-150 ℃, 100-200 ℃, 150-250 ℃, 250-300 ℃, wherein the heating rate of each temperature section is 25 ℃/min, and the final temperature is kept constant for 5min, synchronously detecting the shale oil content and the molecular composition thereof, quantifying by an external standard method, utilizing analysis parameter indexes such as fraction oil content exploration, fraction molecular composition, light-weight ratio and the like, evaluating the oil content, fluidity and properties of shale, achieving the purposes of evaluating a shale oil reservoir and predicting the fluidity, and meeting the requirements of shale oil on geological experimental technology. Provides important geological experimental basis for exploration and production such as shale oil 'quadric' evaluation, 'dessert' optimization and the like.)

1. A synchronous analysis method for oil content and molecular composition of shale fractions comprises the following steps:

1) collecting a shale oil exploration drilling coring rock sample, sampling and freezing and storing the rock sample in a drilling site or a core library to obtain a shale experimental sample;

2) opening a carrier gas and chemical workstation power switch of a shale oil content and fine component synchronous experimental analysis device, switching on air and hydrogen, and setting shale oil fraction content and molecular composition synchronous analysis condition parameters;

3) when the device in the step 2) reaches the set value of the analysis condition parameters, accurately weighing the mudstone standard substance for experimental analysis to obtain mudstone standard substance fraction and molecular composition synchronous analysis data thereof;

4) coarsely crushing the shale sample obtained in the step 1), weighing the sample, and carrying out experimental analysis according to the same analysis condition parameters of shale standard substances to obtain shale oil fraction and molecular composition synchronous analysis data thereof;

5) carrying out external standard method quantification on the shale sample analysis data obtained in the step 4) by using the shale standard substance analysis data obtained in the step 3) to obtain shale fractions and molecular composition analysis parameters thereof;

6) and 5) evaluating the oil content of the shale fraction and the molecular composition characteristics thereof, the oil content of the shale fraction and the fluidity of the shale by using the shale fraction and the molecular composition analysis parameters thereof obtained in the step 5).

2. The method for synchronously analyzing the oil content and the molecular composition of the shale fraction as claimed in claim 1, wherein the method comprises the following steps: the shale oil content and fine component synchronous experimental analysis device in the step 2) comprises four parts, namely an oil content detection unit (1), a trapping and heat releasing unit (2), a fine component detection unit (3) and an oil content and fine component synchronous analysis control unit (4);

the synchronous analysis control unit (4) comprises an analysis control and data processor and a chemical workstation (47), and the analysis control and data processor and the chemical workstation (47) are sequentially connected with a six-way valve controller b (46), an electromagnetic valve controller (45), a trapping and hot-trap controller (44), a six-way valve controller a (43), a negative pressure pump (42), a pyrolysis furnace controller (41) and a sample injection controller (40);

the oil content detection unit (1) comprises a sample injector (10), a pyrolysis furnace (11), a quantitative flow divider (12) and an FID detector a (13), wherein the sample injector (10), the pyrolysis furnace (11), the quantitative flow divider (12) and the FID detector a (13) are communicated through a pressure-resistant pipeline in sequence; one path of the FID detector (13) is connected with an electronic flowmeter a (14), a pressure stabilizing valve a (15) and an air pipeline through pressure-resistant pipelines, and the other path of the FID detector is connected with an electronic flowmeter b (16), a pressure stabilizing valve b (17) and a hydrogen pipeline; the sample inlet end of the sample injector (10) is connected with an electronic flowmeter c (18), a pressure stabilizing valve c (19) and a carrier gas pipeline;

one end of an electronic flowmeter d (26) used for trapping by the trapping and heat releasing unit (2) is connected with the quantitative flow divider (12) of the oil content detection unit (1) through a pressure-resistant pipeline, and the other end of the electronic flowmeter d (26) is connected with a six-way valve a (20), an electromagnetic valve (21), a trapping pipe (22), the six-way valve a (20), an electronic flowmeter e (27) and a negative pressure pump (42) of the synchronous analysis control unit (4) through a pressure-resistant pipeline; one end of an electronic flowmeter d (26) during heat release is connected with the quantitative flow divider (12) of the oil content detection unit (1) through a pressure-resistant pipeline, and the other end of the electronic flowmeter d is connected with the six-way valve a (20), the electromagnetic valve (21), the collecting pipe (22), the six-way valve a (20), the six-way valve b (25) and the analysis column (30) of the fine component detection unit (3) through the pressure-resistant pipeline;

the fine component detection unit (3) comprises an analysis column (30), the sample introduction end of the analysis column (30) is connected with a six-way valve b (25) of the trapping and heat release unit (2), and the outlet end of the analysis column is connected with a FID detector b (31); one path of the FID detector b (31) is connected with the electronic flowmeter f (32), the pressure stabilizing valve d (33) and the air pipeline through pressure-resistant pipelines, and the other path of the FID detector b (31) is connected with the electronic flowmeter g (34), the pressure stabilizing valve e (35) and the hydrogen pipeline.

3. The method for synchronously analyzing the oil content and the molecular composition of the shale fraction as claimed in claim 1, wherein the method comprises the following steps: and (2) freezing and storing the shale sample in the step 1) by adopting liquid nitrogen.

4. The method for synchronously analyzing the oil content and the molecular composition of the shale fraction as claimed in claim 1, wherein the method comprises the following steps: setting working and experimental analysis condition parameters in the step 2) mainly from the initial temperature of the pyrolysis furnace to the final temperature of 30-90 ℃ (S)_1-0）、90℃～150℃（S_1-1）、100℃～200℃（S_1-2）、150℃～250℃（S_1-3）、250℃～300℃（S_1-4)5 temperature sections, wherein the heating rate of each temperature section is 25 ℃/min, the final temperature is constant for 5min, and the freezing enrichment time of each temperature section is S_1-0Is 7.4min, S_1-1Is 7.4min, S_1-2Is 7min and S_1-3Is 7min and S_1-4Is 7min, the heat release temperature is 300 ℃, the heat release time is 10min, S_1-0The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 100 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-1The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 160 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-2The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 210 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-3The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 260 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-4The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 310 ℃ and the constant temperature is 10min, and the heating rate is 5 ℃/min.

5. The method for synchronously analyzing oil content and fine components in shale according to claim 1, wherein the method comprises the following steps: and 3) weighing 50g of mudstone standard substance for analysis.

6. The method for synchronously analyzing oil content and fine components in shale according to claim 1, wherein the method comprises the following steps: and 4) coarsely crushing the shale, and weighing 50g of sample with the particle size of 1-3 mm for analysis.

7. The method for synchronously analyzing oil content and fine components in shale according to claim 1, wherein the method comprises the following steps: step 4) fractionating the shale into gas S_1-0Gasoline S_1-1Kerosene S_1-2Diesel oil S_1-3Heavy oil S_1-4The content (mg/g,%).

8. The method for synchronously analyzing oil content and fine components in shale according to claim 1, wherein the method comprises the following steps: the experimental analysis parameter of the step 5) is mainly shale fraction gas (S)_1-0) Gasoline (S)_1-0) Kerosene (S)_1-0) Diesel oil (S)_1-0) And heavy oil (S)_1-0) Content (mg/g,%), fine component content (mg/g,%), carbon number range, light-weight ratio (steam + coal + firewood)/heavy, and the like.

9. The method for synchronously analyzing oil content and fine components in shale according to claim 1, wherein the method comprises the following steps: and 6) evaluating the oil content and fine component characteristics of the shale reservoir according to the drilling site and the frozen samples of the core library respectively, evaluating the oil content and the mobility of the shale according to different wells and maturity under the same experimental analysis condition, and setting the light-weight ratio parameter to be more than or equal to 2.6 as a shale oil mobility dessert evaluation boundary.

Technical Field

The invention relates to the technical field of unconventional oil and gas exploration of oil fields, in particular to a method for synchronously analyzing the oil content and the molecular composition of shale fractions.

Background

The breakthrough of shale oil in north america brings a new technical revolution of the global oil and gas industry, and leads the development of shale oil exploration to be hot in the world. The shale oil reservoir 'quadric' (reservoir, oil-bearing, fluidity and compressibility) evaluation is important research content and basis of shale oil exploration and development, while the oil-bearing and fluidity evaluation is key of the exploration and development and has important significance for shale oil 'dessert' optimization, reserve and resource quantity evaluation and other exploration and development.

The evaluation method of the oil content of shale oil and compact oil reservoirs is reported in the literature, and is referred to as ' rock pyrolysis analysis ' such as Wu Li (Wu), Zhang Zheng Ling, Li bin and the like (national standard GB/T18602 one 2012 of the people's republic of China, 7 months and 1 day 2013); (2) "petroleum and deposited organic matter hydrocarbon gas chromatography analysis methods" of Shatingrong, Li, Zhang He, etc. (China's republic of China petroleum and gas industry standard SY/T5779 one-year 2008, 12 months and 1 day 2008); (3) "Jiyang depression shale oil reservoir substance component oil property control law" (oil and gas ground)Recovery of biomass, stage 1 in 2019); (4) nintendo, wenyi hua, zheng lei and the like "pre-stack inverted tight sandstone reservoir prediction and oil-gas bearing detection" (Tu ha oil gas, stage 1 of 2012); (5) the zhangjin "shale oil well logging evaluation method and its applications" (geophysical progress, 3 rd stage 2012); (6) plum blossom, Prunus mume, a "quantitative evaluation and prediction of oil content of Dongying depressed lithologic oil and gas reservoir" (oil and gas geology and recovery ratio, 3 rd stage 2006), and the like. The (1) adopts ROCK-EVAL 6 type produced by Wanqi France company or 'crude oil ROCK evaluation instrument' produced by domestic manufacturers to detect parameters such as ROCK pyrolysis S1, S2, Tmax and the like, and evaluates the oil content of the reservoir and shale; analyzing saturated hydrocarbon, aromatic hydrocarbon and crude oil full hydrocarbon components and parameters in the rock chloroform extract by adopting a gas chromatography, and evaluating the types, maturity, oil-containing characteristics and the like of crude oil and deposited organic matter matrixes; performing crude oil occurrence state and substance component analysis on shale oil reservoirs of upper sub-section of the four-depression-in-sand section and lower sub-section of the three-depression-in-sand section by adopting a petrology and geochemistry analysis means, wherein the analysis technology comprises shale oil fluorescent sheet characteristics and scanning electron microscope occurrence state analysis technology; the step (4) adopts the integrated technology of seismic data amplitude preservation processing and prestack inversion to predict the oil-gas content of the compact and shale reservoir, which is usually the oil-gas content evaluation on the macroscopic scale; the oil content evaluation of shale oil is carried out by utilizing the logging method, and because the storage space of a compact reservoir is small, the oil and gas information detected by the logging technology is weak, and the oil content evaluation difficulty is high; and (6) establishing a quantitative prediction model of the oil content of the lithologic trap by adopting a mathematical geology method of stepwise regression and variable elimination. Therefore, the experimental apparatus and method at home and abroad can only realize the analysis of the oil content or hydrocarbon components of the shale and the compact sandstone, but cannot realize the oil content (pyrolysis S) of the shale₁) The evaluation of the oil content and the fluidity of the shale reservoir is restricted by the synchronous experimental analysis and evaluation of different fraction contents and the hydrocarbon molecular composition thereof.

Disclosure of Invention

The invention aims to overcome the defect that the prior experiment in the background technology can not realize the oil content (pyrolysis S) of the shale₁) The synchronous experimental analysis and evaluation of different fraction contents and hydrocarbon molecular compositions thereof consequently restrictThe evaluation of the oil content and the fluidity of the shale reservoir, and provides a synchronous analysis method for the oil content of shale fractions and the molecular composition thereof. The shale fraction oil content and molecular composition synchronous analysis method can evaluate the oil content, fluidity and properties of shale, achieve the purposes of shale oil reservoir evaluation and fluidity prediction, and meet the requirements of shale oil exploration on geological experimental technology.

The invention can solve the problems by the following technical scheme: a synchronous analysis method for oil content and molecular composition of shale fractions comprises the following steps:

1) collecting a shale oil exploration drilling coring rock sample, sampling and freezing and storing the rock sample in a drilling site or a core library to obtain a shale experimental sample;

2) opening a carrier gas and chemical workstation power switch of a shale oil content and fine component synchronous experimental analysis device, switching on air and hydrogen, and setting shale oil fraction content and molecular composition synchronous analysis condition parameters;

3) when the device in the step 2) reaches the set value of the analysis condition parameters, accurately weighing the mudstone standard substance for experimental analysis to obtain mudstone standard substance fraction and molecular composition synchronous analysis data thereof;

4) coarsely crushing the shale sample obtained in the step 1), weighing the sample, and carrying out experimental analysis according to the same analysis condition parameters of shale standard substances to obtain shale oil fraction and molecular composition synchronous analysis data thereof;

5) carrying out external standard method quantification on the shale sample analysis data obtained in the step 4) by using the shale standard substance analysis data obtained in the step 3) to obtain shale fractions and molecular composition analysis parameters thereof;

6) and 5) evaluating the oil content of the shale fraction and the molecular composition characteristics thereof, the oil content of the shale fraction and the fluidity of the shale by using the shale fraction and the molecular composition analysis parameters thereof obtained in the step 5).

And (2) freezing and storing the shale sample in the step 1) by adopting liquid nitrogen.

The step 2) setting working and experimental analysis condition parameters mainly comprise the initial temperature of the pyrolysis furnaceTo final temperature of 30-90 ℃ (S)_1-0)、90℃～150℃(S_1-1)、100℃～200℃(S_1-2)、150℃～250℃(S_1-3)、250℃～300℃(S_1-4)5 temperature sections, wherein the heating rate of each temperature section is 25 ℃/min, the final temperature is constant for 5min, and the freezing enrichment time of each temperature section is S_1-0Is 7.4min, S_1-1Is 7.4min, S_1-2Is 7min and S_1-3Is 7min and S_1-4Is 7min, the heat release temperature is 300 ℃, the heat release time is 10min, S_1-0The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 100 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-1The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 160 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-2The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 210 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-3The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 260 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-4The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 310 ℃ and the constant temperature is 10min, and the heating rate is 5 ℃/min.

And 3) weighing 50g of mudstone standard substance for analysis.

And 4) coarsely crushing the shale, and weighing 50g of sample with the particle size of 1-3 mm for analysis.

The shale fraction in the step 4) is gas S_1-0Gasoline S_1-1Kerosene S_1-2Diesel oil S_1-3Heavy oil S_1-4The content (mg/g,%).

The experimental analysis parameter of the step 5) is mainly shale fraction gas (S)_1-0) Gasoline (S)_1-0) Kerosene (S)_1-0) Diesel oil (S)_1-0) And heavy oil (S)_1-0) Content (mg/g,%), fine component content (mg/g,%), carbon number range, light-weight ratio (steam + coal + firewood)/heavy, and the like.

And 6) evaluating the oil content and fine component characteristics of the shale reservoir according to the drilling site and the frozen samples of the core library respectively, evaluating the oil content and the mobility of the shale according to different wells and maturity under the same experimental analysis condition, and setting the light-weight ratio parameter to be more than or equal to 2.6 as a shale oil mobility dessert evaluation boundary.

Compared with the background technology, the invention has the following beneficial effects: the invention provides a shale oil content and molecular composition synchronous analysis method, which mainly utilizes a shale oil content and fine component synchronous experimental analysis device, adopts 5 temperature sections of 30-90 ℃, 90-150 ℃, 100-200 ℃, 150-250 ℃, 250-300 ℃, the temperature rise rate of each temperature section is 25 ℃/min, the final temperature is constant for 5min, the shale oil content is cut into 5 main fractions of gas, gasoline, kerosene, diesel oil and heavy oil, the shale oil content and the molecular composition thereof are synchronously detected and quantified by an external standard method, the analytical parameter indexes of the oil content, the molecular composition of the fractions, the light-weight ratio and the like are utilized, the method has the advantages that the oil content, the mobility and the property of the shale are evaluated, the purposes of shale oil reservoir evaluation and mobility prediction are achieved, and the requirement of shale oil exploration on a geological experiment technology is met.

Description of the drawings:

FIG. 1 is a device for synchronously testing and analyzing oil content and fine components of shale according to the invention;

FIG. 2 is a synchronous analysis spectrogram of oil content and molecular composition of shale fractions of a field frozen sample in an embodiment of the invention;

FIG. 3 is a synchronous analysis spectrum of the oil content of the fraction and the molecular composition of the unfrozen shale sample in the embodiment of the invention.

In the figure:

1-oil content detection unit, 10-sample injector, 11-pyrolysis furnace, 12-quantitative flow divider, 13-FID detector a, 14-electronic flow meter a, 16-electronic flow meter b, 18-electronic flow meter c, 15-pressure stabilizing valve a, 17-pressure stabilizing valve b, 19-pressure stabilizing valve c;

2-trapping and heat releasing unit, 20-six-way valve a, 25-six-way valve b, 21-electromagnetic valve, 22-trapping pipe, 23-cold trap (trapping trap), 24-heat releasing trap, 26-electron flowmeter d, 27-electron flowmeter e;

3-fine component detection unit, 30-analytical column, 31-FID detector b, 32-electronic flow meter f, 34-electronic flow meter g, 33-pressure maintaining valve d, 35-pressure maintaining valve e;

4-oil content and fine component synchronous analysis control unit, 40-sample injector controller, 41-pyrolysis furnace controller, 42-negative pressure pump, 43-six-way valve controller a, 46-six-way valve controller b, 44-trapping and hot-trap controller, 45-solenoid valve controller, 47-analysis control and data processor and chemical workstation.

The specific implementation mode is as follows:

the invention will be further described with reference to the following drawings and specific embodiments:

the invention mainly provides a synchronous analysis method for oil content and molecular composition of shale oil fraction, which mainly utilizes a synchronous experimental analysis device for the oil content and fine components of shale, adopts 5 temperature sections of 30-90 ℃, 90-150 ℃, 100-200 ℃, 150-250 ℃, 250-300 ℃, the heating rate of each temperature section is 25 ℃/min, and the final temperature is kept constant for 5min, cuts the shale oil content into 5 main fractions which are respectively gas, gasoline, kerosene, diesel oil and heavy oil, synchronously detects the oil content and the molecular composition of the shale oil fraction, quantifies the shale oil content and the molecular composition by an external standard method, utilizes the analysis parameter indexes such as the oil content of the fraction, the molecular composition of the fraction, the light-weight ratio and the like to evaluate the oil content, the fluidity and the property of the shale oil, and meets the requirements of shale oil exploration on geological experimental technology.

First, analytical equipment

The synchronous analysis of the oil content and the molecular composition of the shale fraction adopts a synchronous experimental analysis device for the oil content and the fine components of the shale.

As shown in fig. 1, the shale oil content and fine component synchronous experimental analysis device comprises an oil content detection unit 1, a capture and heat release unit 2, a fine component detection unit 3, and an oil content and fine component synchronous analysis control unit 4;

the synchronous analysis control unit 4 comprises an analysis control and data processor and a chemical workstation 47, the analysis control and data processor and the chemical workstation 47 are connected with the fine component detection unit 3 through signal lines and communication interfaces, and the analysis control and data processor and the chemical workstation 47 are further connected with a six-way valve controller b46, an electromagnetic valve controller 45, a trapping and heat-trap controller 44, a six-way valve controller a43, a negative pressure pump 42, a pyrolysis furnace controller 41 and a sample injection controller 40 in sequence.

The oil content detection unit 1 mainly comprises a sample injector 10, a pyrolysis furnace 11, a quantitative flow divider 12 and an FID detector a13, wherein the sample injector 10, the pyrolysis furnace 11, the quantitative flow divider 12 and the FID detector a13 are sequentially communicated through a pressure-resistant pipeline; one path of the FID detector 13 is connected with an electronic flowmeter a14, a pressure stabilizing valve a15 and an air pipeline through pressure-resistant pipelines, and the other path of the FID detector is connected with an electronic flowmeter b16, a pressure stabilizing valve b17 and a hydrogen pipeline; the sample inlet end of the sample injector 10 is connected with an electronic flow meter c18, a pressure stabilizing valve c19 and a gas carrying pipeline; meanwhile, the sample injector 10 and the pyrolysis furnace 11 are respectively connected with a sample injection controller 40 and a pyrolysis furnace controller 41 of the synchronous analysis control unit 4 through signal lines and communication interfaces; the other outlet of the quantitative flow divider 12 is connected with an electronic flowmeter d26 of the trapping and heat releasing unit 2 through a pressure-resistant pipeline;

one end of an electronic flowmeter d26 used for trapping by the trapping and heat releasing unit 2 is connected with the quantitative flow divider 12 of the oil content detecting unit 1 through a pressure-resistant pipeline, and the other end is connected with a six-way valve a20, an electromagnetic valve 21, a trapping pipe 22, a six-way valve a20, an electronic flowmeter e27 and a negative pressure pump 42 of the synchronous analysis control unit 4 through a pressure-resistant pipeline; one end of an electronic flowmeter d26 during heat release is connected with the quantitative flow divider 12 of the oil content detection unit 1 through a pressure-resistant pipeline, and the other end is connected with the six-way valve a20, the electromagnetic valve 21, the collecting pipe 22, the six-way valve a20, the six-way valve b25 and the analysis column 30 of the fine component detection unit 3 through a pressure-resistant pipeline; meanwhile, the six-way valve a20, the electromagnetic valve 21, the cold trap 23, the heat release trap 24 and the six-way valve b25 are respectively connected with the six-way valve controller a43, the electromagnetic valve controller 45, the trapping and heat trap controller 44 and the six-way valve controller b46 of the synchronous analysis control unit 4 through signal lines and communication interfaces.

The fine component detection unit 3 comprises an analytical column 30, the sample inlet end of the analytical column 30 is connected with a six-way valve b25 of the trapping and heat releasing unit 2, and the outlet end is connected with a FID detector b 31; one path of the FID detector b31 is connected with an electronic flowmeter f32, a pressure stabilizing valve d33 and an air pipeline through pressure resisting pipelines, and the other path of the FID detector b31 is connected with an electronic flowmeter g34, a pressure stabilizing valve e35 and a hydrogen pipeline; meanwhile, the fine component detection unit 3 is connected to the analysis control and data processor of the synchronous analysis control unit 4 and the chemical workstation 47 through signal lines and a communication interface, respectively.

The oil content detection unit 1 is connected with an electronic flowmeter d26, a six-way valve a20, an electromagnetic valve 21, a collection pipe 22 and a six-way valve b25 of the collection and heat release unit 2 through a quantitative flow divider 12, and then is connected with an analysis column 30 and a FID detector b31 of a fine component detection unit 3; meanwhile, the analysis control and data processor and chemical workstation 47 of the synchronous analysis control unit 4 are connected with the fine component detection unit 3, the six-way valve controller a43, the six-way valve controller b46, the electromagnetic valve controller 45, the trapping and hot trap controller 44, the negative pressure pump 42, the trapping and heat release unit 2, the pyrolysis furnace controller 41, the sample injector controller 40 and the oil content detection unit 1, so that the automatic control of the synchronous detection process of the oil content and the fine component of the shale is realized.

The oil content detection unit 1 mainly comprises a sample injector 10, a pyrolysis furnace 11, a quantitative flow divider 12, an FID detector a13, an electronic flow meter a14, an electronic flow meter b16, an electronic flow meter c18, a pressure stabilizing valve a15, a pressure stabilizing valve b17 and a pressure stabilizing valve c19 which correspond to each other and are communicated through a pressure resisting pipeline; the injector 10 is automatically turned off or on the pyrolysis furnace and the sample is topped or backed off by the injector controller 40 upon instructions from the analysis control and data processor and chemical workstation 47; the pyrolysis furnace 11 automatically realizes the automatic control of the temperature of the pyrolysis furnace according to the instructions given by the analysis control and data processor and the chemical workstation 47 by the pyrolysis furnace controller 41, the maximum pyrolysis temperature is 800 ℃, and the temperature control precision is 0.1 ℃; the quantitative flow divider 12 automatically realizes the quantitative flow division of the shale oil component by the negative pressure pump 42 according to the instructions given by the analysis control and data processor and the chemical workstation 47; the FID detector a13 automatically detects the oil content of shale or any fractional fraction by instructions from the analysis control and data processor and chemical workstation 47.

The trapping and heat releasing unit 2 mainly comprises a six-way valve a20, a six-way valve b25, an electromagnetic valve 21, a trapping pipe 22, a cold trap 23, a heat releasing trap 24, an electronic flowmeter d26 and an electronic flowmeter e27 which correspond to each other and are communicated through pressure-resistant pipelines; the negative pressure pump 42, the six-way valve a20, the six-way valve controller a43, the electromagnetic valve controller 45 of the electromagnetic valve 21, the cold trap 23 and the trapping and heat releasing controller 44 automatically realize the enrichment of shale oil or any fraction component in the trapping pipe according to the instructions given by the analysis control and data processor and the chemical workstation 47, and the lowest freezing and trapping temperature is-196 ℃; the six-way valve a20 is composed of a six-way valve controller a43, an electromagnetic valve controller 45 of an electromagnetic valve 21, a heat release trap 24 is composed of a trapping and heat release controller 44, a six-way valve b25 is composed of a six-way valve controller b46, and heat release of shale oil or any fraction component in the trapping pipe is automatically realized according to instructions given by an analysis control and data processor and a chemical workstation 47, wherein the maximum heat release temperature is 800 ℃, and the temperature control precision is 0.1 ℃; the six-way valve a20 is composed of a six-way valve controller a43, an electromagnetic valve controller 45 of an electromagnetic valve 21, a heat release trap 24 is composed of a trapping and heat release controller 44, a six-way valve b25 is composed of a six-way valve controller b46, and according to instructions given by an analysis control and data processor and a chemical workstation 47, heating, purification and emptying of the trapping and heat release unit 2 are automatically realized; the six-way valve b25 and the carrier gas of the trapping and heat releasing unit 2 are automatically aged and purified by the analytical column 30 of the fine constituent detecting unit 3 by the six-way valve controller b46, the analytical column 30 and the FID detector b31 according to instructions given from the analytical control and data processor and the chemical workstation 47.

The fine component detection unit 3 mainly comprises an analysis column 30, an FID detector b31, an electronic flowmeter f32, an electronic flowmeter g34, a pressure stabilizing valve d33 and a pressure stabilizing valve e35 which are correspondingly communicated through a pressure resisting pipeline; the analysis column 30 and the FID detector b31 automatically realize the separation and detection of shale oil or any fraction fine molecular components according to the instructions given by the analysis control and data processor and the chemical workstation 47;

the synchronous analysis control unit 4 mainly comprises a sample injection controller 40, a pyrolysis furnace controller 41, a negative pressure pump 42, a six-way valve controller a43, a six-way valve controller b46, a trapping and hot trap controller 44, an electromagnetic valve controller 45, an analysis control and data processor and a chemical workstation 47, which correspond to each other and are connected through a signal line and a communication interface, so that the automatic control of synchronous experimental analysis of oil content and fine components of the shale is realized, and the detection data recording and data processing are realized.

When the device is used, a carrier gas, a power supply and a chemical workstation switch of the shale oil content and fine component synchronous experimental analysis device are turned on, air and hydrogen are switched on, working and analysis parameters of the device are respectively set, and all set working and analysis parameter values are reached; placing the enrichment tube 22 completely in the cold trap 23 liquid nitrogen, weighing milligram samples, and placing the milligram samples into the sample injector 10; the analysis is initiated, the sample is tested, and the control and data processor and chemical workstation 47 automatically controls and records the analytical data.

Method for synchronously analyzing oil content and molecular composition of shale fraction

1. Shale fraction oil content analysis condition

Main analysis conditions of oil content of shale: the pyrolysis furnace is set with 5 temperature sections at 30-90 ℃ (S)_1-0Gas) at 90-150 deg.C (S)_1-1Gasoline) at 150-200 deg.C (S)_1-2Kerosene) at 200-250 deg.C (S)_1-3Diesel oil) at 250-300 deg.C (S)_1-4Heavy oil), the temperature programming rate of each temperature section is 25 ℃/min, and the final temperature is kept constant for 5 min; the purity of carrier gas helium is 99.999%, and the working pressure is 0.90-1.00 MPa; the purity of the fuel gas hydrogen is 99.999 percent, and the working pressure is 0.20-0.30 MPa; the working pressure of combustion-supporting gas air is 0.50-0.60 MPa; and (3) crushing the sample to obtain a particle size of 1-3 mm, weighing the sample amount to 50mg, and quantifying by an external standard method.

2. Shale oil fraction hydrocarbon enrichment and heat release conditions

The main enrichment conditions are as follows: adopting liquid nitrogen to freeze and enrich, completely submerging the collecting pipe by liquid nitrogen, and freezing and enriching time S_1-0Is 7.4min, S_1-1Is 7.4min, S_1-2Is 7min and S_1-3Is 7min and S_1-4It is 7 min. The main conditions of heat release are as follows: the heat release temperature is 300 ℃, the temperature control precision is 0.1 ℃, and the heat release time is 10 min; the temperature of the trapping and heat releasing unit pipeline and the valve is 300 ℃.

3. Shale oil fraction hydrocarbon molecular analysis condition

The main conditions for analyzing the molecular components of the fraction comprise that an analytical column is 50m × 0.20mm × 0.5.5 mu m, the temperature of an FID detector is 320 ℃, the flow rate of fuel gas is 45ml/min, the flow rate of combustion-supporting gas is 450ml/min, and S_1-0The column temperature is 35 ℃, the temperature is kept for 5min, and the temperature is increased to 5 ℃/minKeeping the temperature at 100 deg.C for 10 min; s_1-1The column temperature is 35 ℃, the temperature is kept for 5min, the temperature is raised to 160 ℃ at the speed of 5 ℃/min, and the temperature is kept for 10 min; s_1-2The column temperature is 35 ℃, the temperature is kept for 5min, the temperature is raised to 210 ℃ at the speed of 5 ℃/min, and the temperature is kept for 10 min; s_1-3The column temperature is 35 ℃, the temperature is kept for 5min, the temperature is raised to 260 ℃ at the speed of 5 ℃/min, and the temperature is kept for 10 min; s_1-4The column temperature is 35 ℃, the temperature is kept for 5min, the temperature is increased to 310 ℃ at the speed of 5 ℃/min, and the temperature is kept for 10 min.

Qualitative and quantitative determination: standard sample, retention time and literature qualification can be carried out, and the gas, gasoline, kerosene, diesel oil and heavy oil fraction contents (mg/g,%) of shale oil, hydrocarbon molecular composition (mg/g,%) data and geological analysis parameters can be obtained.

The method for synchronously analyzing the oil content and the molecular composition of the shale fraction comprises the following steps:

1) collecting a shale oil exploration drilling coring rock sample, and performing freeze preservation on a drilling site or a core library sample by using liquid nitrogen to obtain a shale experimental sample;

2) opening a power switch of a carrier gas and chemical workstation of a synchronous experimental analysis device for oil content and fine components of shale, switching on air and hydrogen, and adjusting the temperature to 30-90 ℃ (S) according to the initial temperature of the pyrolysis furnace to the final temperature_1-0)、90℃～150℃(S_1-1)、100℃～200℃(S_1-2)、150℃～250℃(S_1-3)、250℃～300℃(S_1-4)5 temperature sections, wherein the heating rate of each temperature section is 25 ℃/min, the final temperature is constant for 5min, and the freezing enrichment time of each temperature section is S_1-0Is 7.4min, S_1-1Is 7.4min, S_1-2Is 7min and S_1-3Is 7min and S_1-4Is 7min, the heat release temperature is 300 ℃, the heat release time is 10min, S_1-0The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 100 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-1The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 160 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-2The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 210 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-3The column temperature is 35 ℃ and the constant temperature is 5min, the final temperature is 260 ℃ and the constant temperature is 10min, the heating rate is 5 ℃/min, S_1-4The column temperature is 35 ℃, the constant temperature is 5min, and the final temperature is 310Keeping the temperature at 10min, heating at a rate of 5 ℃/min, and setting synchronous analysis condition parameters of shale oil fraction content and molecular composition;

3) when the device in the step 2) reaches the set value of the analysis condition parameters, accurately weighing 50g of mudstone standard substance for experimental analysis to obtain synchronous analysis data of the mudstone standard substance fraction and the molecular composition thereof;

4) coarsely crushing the frozen shale sample in the step 1), weighing 50g of sample with the particle size of 1-3 mm, and carrying out experimental analysis according to the same analysis condition parameters of the shale standard substance to obtain shale oil fraction gas S_1-0Gasoline S_1-1Kerosene S_1-2Diesel oil S_1-3Heavy oil S_1-4And its molecular composition synchronous analysis data;

5) performing external standard method quantification on the shale sample analysis data obtained in the step 4) by using the shale standard substance analysis data obtained in the step 3) to obtain shale fraction gas S_1-0Gasoline S_1-1Kerosene S_1-2Diesel oil S_1-3Heavy oil S_1-4Analysis parameters of content (mg/g,%) and molecular composition (mg/g,%);

6) utilizing the shale fraction gas S obtained in the step 5)_1-0Gasoline S_1-1Kerosene S_1-2Diesel oil S_1-3Heavy oil S_1-4Content (mg/g,%) and molecular composition (mg/g,%) analysis parameters, and evaluation of oil content of shale fraction and molecular composition characteristics thereof, oil content of shale and fluidity is performed.