Method for simulating influence of montmorillonite clay mineral water on organic matter pyrolysis hydrocarbon generation

Abstract

The invention provides a method for simulating the influence of montmorillonite clay mineral water on organic matter pyrolysis hydrocarbon generation, and belongs to the technical field of organic matter pyrolysis. The method comprises the following steps: heating montmorillonite to obtain dehydrated montmorillonite, mixing organic matters and the dehydrated montmorillonite in an argon atmosphere and a dry environment, transferring a mixed sample into a gold tube, and loading the sample; putting the gold tube into an iron reaction kettle, filling the reaction kettle with water, and cooling after heating reaction; putting the cooled gold tube into a gas collecting device, and calculating the amount of substance of gas according to an ideal gas state equation; the collected gas is subjected to GC analysis to obtain the percentage of each gas, the yield of each gas is calculated by combining the amount of substance of the gas, and the influence of the montmorillonite clay endogenous water on hydrocarbon generation by thermal decomposition of organic matters is evaluated. Under the condition that only the unified boundary condition of clay mineral water is changed, a verifiable judgment system of'endogenous water type-product spectrum characteristic-reaction channel 'is established for the first time.

Description

Technical Field

[0001] This invention relates to the field of organic matter pyrolysis technology, and in particular to a method for simulating the effect of montmorillonite clay mineral water on hydrocarbon generation from organic matter pyrolysis. Background Technology

[0002] Clay minerals (such as montmorillonite and illite) are widely coexisting in organic-rich sedimentary systems and are believed to influence the decomposition pathways, product composition, and overall conversion efficiency of organic matter during pyrolysis / thermal evolution. Existing studies on clay mineral + organic matter systems mostly focus on comparing the thermal decomposition products and decomposition efficiency of organic matter based on factors such as "whether water is added," "temperature gradient and reaction temperature," or "differences in clay mineral types." However, the release of adsorbed water and interlayer water by clay during heating and their potential effects are often overlooked. Nominally dry systems often transform into uncontrolled aqueous systems at high temperatures due to the release of water from clay minerals, affecting both mechanistic assessments and the comparability between different studies.

[0003] Current technologies lack a technical approach to treat clay mineral water as an independent, characterizable variable and conduct group control studies under a unified sample and evaluation system. Therefore, it is necessary to establish an experimental technique with clay mineral water as the core variable, which is simple to operate, has traceable conditions, and provides intuitive evaluation methods, specifically for observing and comparing the effects of clay mineral water on the efficiency of hydrocarbon generation from the pyrolysis of organic matter catalyzed by clay minerals. Summary of the Invention

[0004] The purpose of this invention is to provide a method for simulating the effect of montmorillonite clay mineral water on the pyrolysis of organic matter and hydrocarbon generation, addressing the shortcomings of existing technologies.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for simulating the effect of montmorillonite clay mineral water on the pyrolysis of organic matter and hydrocarbon generation, comprising the following steps: 1) Montmorillonite was subjected to low-temperature heating and high-temperature heating respectively to obtain dehydrated montmorillonite: montmorillonite with adsorbed water removed and montmorillonite with mineral water removed; 2) Organic matter and dehydrated montmorillonite are mixed in an argon atmosphere and a dry environment to obtain a mixed sample, which is then transferred to a gold tube for loading. 3) Insert the gold tube into the iron reactor, fill the iron reactor with water, heat the reaction and then cool it; 4) After cooling, the gold tube is placed in a gas collection device, which is a glass collection device; the glass collection device is equipped with a puncture needle and a three-valve. After evacuating the gas collection device, record the gas pressure as P1; after the puncture needle pierces the gold tube and the reading stabilizes, record the gas pressure as P2; calculate the amount of substance of the gas based on the ideal gas law. The collected gases were analyzed by GC to obtain the percentage of each gas. The yield of each gas was calculated based on the amount of substance of the gas, and the impact of endogenous water in montmorillonite clay on the thermal decomposition of organic matter to generate hydrocarbons was evaluated.

[0006] Preferably, the temperature of the low-temperature heating in step 1) is 100~200℃, the temperature of the high-temperature heating is 200~300℃, and the time for the low-temperature heating and the high-temperature heating are independent and are 10~14h.

[0007] Preferably, the humidity of the drying environment in step 2) is ≤5%, the purity of the organic matter is ≥98%, and the organic matter contains octadecanoic acid.

[0008] Preferably, in step 2), the mass ratio of organic matter to dehydrated montmorillonite is 0.8~1.2:0.8~1.2; the mixing time is 17~23 min, and the mixing is carried out in a glove box.

[0009] Preferably, the gold tube has a length of 55-65 mm, a wall thickness of 0.2-0.3 mm, and an outer diameter of 5-7 mm; the iron reactor is equipped with a stopcock. Before loading the sample, one end of the gold tube is sealed with argon arc welding. After loading the sample, pinch the unsealed end of the gold tube and seal it in a cold water bath.

[0010] Preferably, the heating reaction temperature in step 3) is 330~350℃, the heating reaction time is 8~12 days, and the rate of heating to the heating reaction temperature is 28~32℃ / h.

[0011] Preferably, in step 4), of the three valves of the glass collection device, one valve is connected to the vacuum pump, one valve is connected to the barometer, and one valve is connected to the collection bag.

[0012] Preferably, the ideal gas law is ΔPV = nRT, where ΔP = P2 - P1; V is the equivalent volume of the collection system; T is the temperature of the collected gas in K; R is a constant; and n is the amount of substance.

[0013] Preferably, the formula for calculating the gas yield is as follows: Where G is the gas yield (mL / g); n is the total amount of gas (mol); W is the percentage of this gas in the total gas (%); R is the volume of 1 mol of gas under standard conditions (22.4 L); and M is the mass of the reactants (mg).

[0014] The beneficial effects of this invention are: 1) This invention sets clay mineral water (adsorbed water, interlayer water) as a controllable independent variable, completing mixing and sealing in an inert, low-humidity environment. The mixture is then compared with undehydrated montmorillonite-octadecanoic acid and octadecanoic acid using a uniform heating process, thermal reaction process, and collection method. This method effectively eliminates confounding factors such as environmental humidity, external water addition, and pretreatment differences, ensuring clear experimental boundaries, consistent measurement standards, comparable and traceable data, and providing a stable methodological baseline for clay mineral-organic matter systems and subsequent mechanism verification.

[0015] 2) Existing studies generally fail to include the presence and type of clay mineral water in the controlled variables, easily conflating the clay mineral water effect with exogenous water addition. This invention, by only changing the unified boundary condition of "clay mineral water," establishes for the first time a verifiable discrimination system of "endogenous water type - product spectrum characteristics - reaction pathway": using total hydrocarbon yield to characterize the difference in cracking efficiency; using the branching / normal ratio (e.g., iC4 / nC4, iC5 / nC5) to indicate changes in isomerization-related pathways; and using CO2 yield to judge the strength of the decarboxylation process, etc. This clearly distinguishes the differentiated regulatory effects of different types of clay mineral water on key pathways such as organic matter cracking, isomerization, and decarboxylation, achieving a more scientific, traceable, and comparable quantitative evaluation system for the "water-mineral-organic matter" coupling effect.

[0016] 3) The standardized evaluation path of "clay mineral water effect" formed by this invention can be directly promoted under different clay minerals and organic matter, different temperature-time-ratio conditions, and can be orthogonally combined with factors such as exogenous water / acid and mineral type to carry out mechanism differentiation, providing a general method for high-temperature thermal simulation design, comparative interpretation of experimental conclusions and geological reality, as well as related technical specifications and engineering scale-up. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the glass collecting device of the present invention; Figure 2 This is a schematic diagram of the acrylic glove box sample of the present invention; Figure 3 The gas yields of different systems in Examples 1-2 and Comparative Examples 1-2; Figure 4 The total gaseous hydrocarbon (∑C1-C5) yield and methane (C1) yield of different systems in Examples 1-2 and Comparative Examples 1-2 are given. Figure 5 The olefin / alkane ratios of different systems in Examples 1-2 and Comparative Examples 1-2 are shown. Figure 6 The yield of butane (C4) and the ratio of butane to total gaseous hydrocarbons (C4 / ∑C1-C5) in different systems of Examples 1-2 and Comparative Examples 1-2 are given. Figure 7The ratios of isoparaffins to n-paraffins in different systems of Examples 1-2 and Comparative Examples 1-2 are given, where iC4 is isobutane, nC4 is n-butane, iC5 isopentane, and nC5 is n-pentane. Detailed Implementation

[0018] This invention provides a method for simulating the effect of montmorillonite clay mineral water on the pyrolysis of organic matter and hydrocarbon generation, comprising the following steps: 1) Montmorillonite (MT) was subjected to low-temperature heating and high-temperature heating respectively to obtain dehydrated montmorillonite: montmorillonite with adsorbed water removed and montmorillonite with mineral water removed; 2) Organic matter and dehydrated montmorillonite are mixed in an argon atmosphere and a dry environment to obtain a mixed sample, which is then transferred to a gold tube for loading. 3) Insert the gold tube into the iron reactor, fill the iron reactor with water, heat the reaction and then cool it; 4) After cooling, the gold tube is placed in a gas collection device, which is a glass collection device; the glass collection device is equipped with a puncture needle and a three-valve. After evacuating the gas collection device, record the gas pressure as P1; after the puncture needle pierces the gold tube and the reading stabilizes, record the gas pressure as P2; calculate the amount of substance of the gas based on the ideal gas law. The collected gases were analyzed by GC to obtain the percentage of each gas. The yield of each gas was calculated based on the amount of substance of the gas, and the impact of endogenous water in montmorillonite clay on the thermal decomposition of organic matter to generate hydrocarbons was evaluated.

[0019] In this invention, the temperature of the low-temperature heating in step 1) is preferably 100~200℃, more preferably 120~180℃, and even more preferably 150~160℃; the temperature of the high-temperature heating is preferably 200~300℃, more preferably 220~280℃, and even more preferably 250~260℃; and the time for the low-temperature heating and the high-temperature heating are independent and preferably 10~14h, more preferably 11~13h, and even more preferably 12h.

[0020] During the low-temperature heating and high-temperature heating processes described in this invention, it is preferable to stir once every 2 hours to ensure that montmorillonite with adsorbed water removed and montmorillonite with mineral water removed are obtained.

[0021] In this invention, montmorillonite is heated at a temperature (±20°C) near the first and second dehydration peaks, with reference to DTG data of different types of montmorillonite. Heating at 100~200°C yields montmorillonite with adsorbed water removed, and heating at 200~300°C yields montmorillonite with mineral water removed.

[0022] In this invention, montmorillonite with adsorbed water removed contains interlayer water and structural water, while montmorillonite with mineral water removed contains very little interlayer water and structural water.

[0023] In this invention, the humidity of the drying environment in step 2) is preferably ≤5%, more preferably ≤4%, and even more preferably ≤3%, and the purity of the organic matter is preferably ≥98%, more preferably ≥99%, and even more preferably ≥99.5%; the organic matter preferably contains octadecanoic acid.

[0024] In this invention, the mass ratio of organic matter to dehydrated montmorillonite in step 2) is preferably 0.8~1.2:0.8~1.2, more preferably 0.9~1.1:0.9~1.1, and even more preferably 1:1; the mixing time is preferably 17~23 min, more preferably 19~21 min, and even more preferably 20 min, and the mixing is preferably carried out in a glove box.

[0025] In this invention, the mixing is carried out in an acrylic transparent glove box. A high-purity argon gas cylinder is used to continuously inject argon gas into the glove box at a pressure of 2MPa to replace the air in the glove box. A hygrometer is placed in the glove box to ensure that the humidity is ≤5%. The dehydrated montmorillonite is very easy to reabsorb moisture from the air. An inert and dry environment is conducive to the preservation of dehydrated montmorillonite.

[0026] In this invention, the length of the gold tube is preferably 55-65 mm, more preferably 57-62 mm, and even more preferably 60 mm; the tube wall thickness is preferably 0.2-0.3 mm, more preferably 0.22-0.28 mm, and even more preferably 0.25-0.26 mm; the outer diameter is preferably 5-7 mm, more preferably 5.5-6.5 mm, and even more preferably 6 mm; the iron reactor is equipped with a stopcock. Before loading the sample, one end of the gold tube is sealed with argon arc welding. After loading the sample, pinch the unsealed end of the gold tube and seal it in a cold water bath.

[0027] In this invention, the temperature of the heating reaction in step 3) is preferably 330~350℃, more preferably 335~345℃, and even more preferably 340℃. The heating reaction time is preferably 8~12 days, more preferably 9~11 days, and even more preferably 10 days. The rate of heating to the heating reaction temperature is preferably 28~32℃ / h, more preferably 29~31℃ / h, and even more preferably 30℃ / h.

[0028] In this invention, of the three valves in the glass collection device described in step 4), one valve is connected to a vacuum pump, one valve is connected to a barometer, and one valve is connected to a collection bag.

[0029] In this invention, the ideal gas law is ΔPV = nRT, where ΔP = P2 - P1; V is the equivalent volume of the collection system (pre-calibrated); T is the temperature of the collected gas in K; R is a constant; and n is the amount of substance.

[0030] In this invention, the formula for calculating the gas yield is as follows: Where G is the gas yield (mL / g); n is the total amount of gas (mol); W is the percentage of this gas in the total gas (%); R is the volume of 1 mol of gas under standard conditions (22.4 L); and M is the mass of the reactants (mg).

[0031] This invention provides a method for evaluating the effect of clay mineral water on the catalytic pyrolysis of organic matter in clay to generate hydrocarbons. This method uses the heat treatment of clay minerals as a variable, standardizes the operational procedures for the reaction environment, sample loading, thermal simulation experiments, and product quantification, and constructs a concise and traceable evaluation framework. Its core objective is to investigate the actual role of different types of clay mineral water on the decomposition efficiency and product composition of organic matter during the heating process, ultimately improving the methodological system for this influencing factor in existing research.

[0032] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0033] In the examples and comparative examples, the acrylic transparent glove box was purchased from Hangzhou Bensong New Material Technology Co., Ltd., with a length of 70cm, a width of 50cm, and a height of 50cm; the precision analytical balance was placed in the glove box and was purchased from Qun'an Scientific Instruments (Zhejiang) Co., Ltd., model CEB2055. The gold tube is 60mm long, 0.25mm thick, and 6mm in outer diameter, with one end sealed by argon arc welding. The forced-air drying oven is a Shanghai Yiheng DHG-9145A forced-air drying oven; Octadecanic acid was purchased from Shanghai Maclean Biochemical Technology Co., Ltd., with a purity >99.5%, and no further purification was required; The calcium-based montmorillonite was purchased from Shanlin Shiyu Mineral Products Co., Ltd., with a purity of 99%. The impurities consisted of inseparable fine quartz. The montmorillonite particles had a diameter of 1-10 μm and its chemical structural formula was Ca. 0.2 (Al,Mg)2Si4O 10 (OH)₂·4H₂O, cation exchange capacity is 128.44 cmol(+) kg. -1 ; The collection device is a glass collection device. Of the three valves in the glass collection device, one valve is connected to a vacuum pump, one valve is connected to a barometer, and one valve is connected to a collection bag.

[0034] Example 1 (System C: 150℃ montmorillonite-octadecanoic acid)

[0035] (1) Montmorillonite dehydration

[0036] Take 10g of calcium-based montmorillonite and spread it evenly at the bottom of a 1000mL beaker. Place it in a forced-air drying oven and heat it at 150℃ for 12 hours (stirring once every 2 hours) to ensure that the montmorillonite with adsorbed water is obtained (150℃ MT).

[0037] (2) Montmorillonite-organic matter sample

[0038] Argon gas is continuously injected into the acrylic transparent glove box at a pressure of 2MPa using a high-purity argon cylinder to replace the air in the glove box. A hygrometer is placed in the glove box to ensure that the humidity is 4%, and the glove box is an inert and dry environment.

[0039] The dehydrated montmorillonite was quickly transferred to an inert, dry glove box. Using a precision analytical balance in the glove box, 99.86 mg of dehydrated montmorillonite and 100.41 mg of octadecanoic acid were weighed and mixed in a 100 mL beaker. The mixture was stirred at 200 rpm for 20 min to obtain a mixed sample. The mixed sample was transferred to a gold tube with one end sealed by argon arc welding using a spatula. After the sample was loaded, the unsealed end was pinched to form a temporary seal and removed. Then, the unsealed end was sealed by argon arc welding under cold water bath conditions.

[0040] (3) Thermal simulation experiment

[0041] The welded gold tube was placed into an iron reactor with a stopcock. The iron reactor was then filled with water, the knob was tightened, and the reactor was placed in a muffle furnace. The temperature was increased to 340°C at a rate of 30°C / h and heated at 340°C for 10 days to carry out the reaction. During the reaction, the reactor was rotated every two days to prevent uneven heating. After the heating was completed, the reactor was removed and cooled to room temperature before the gold tube was taken out.

[0042] (4) Gas collection and detection

[0043] The volume of gas collected was calculated to be 43 mL using the drain valve. The cooled gold tube was then placed into the gas collection device, and the gas collection valve of the gas collection device was connected to the gas collection bag. The vacuum pump was turned on and evacuated for 10 minutes at a power of 300 W. After stabilization, the barometer reading P1 was recorded. The gas collection valve and the vacuum valve were closed in sequence. Then, the puncture needle was tightened to puncture the gold tube. After 3 minutes, the gas diffused and stabilized in the collection device, and the barometer reading P2 was recorded at this time. Then, the gas collection valve was opened to allow the gas in the collection device to enter the gas collection bag. The gas collection bag was placed in liquid nitrogen to increase the gas collection efficiency and collection volume until the barometer reading was close to P1, thus completing the gas collection.

[0044] The amount of gas released is calculated based on the ideal gas law ΔPV = nRT, where ΔP = P2 - P1; V is the equivalent volume of the collection system (43 mL); T is the temperature at which the gas is collected, K; R is a constant; and n is the amount of substance.

[0045] Gas detection was performed using a Bruker 450-GC gas chromatograph to determine the percentage content of each type of gas, and the gas yield of each gas was calculated using Formula 1.

[0046] Formula 1

[0047] Where G is the gas yield in mL / g; n is the total amount of gas in mol; W is the percentage of this gas in the total gas in %; R is the volume of 1 mol of gas under standard conditions in 22.4 L; and M is the mass of the reactants in mg.

[0048] Example 2 (System B: 250℃ montmorillonite-octadecanoic acid)

[0049] The heating temperature in the montmorillonite dehydration step of Example 1 was changed from 150℃ to 250℃ to obtain montmorillonite (250℃ MT) with mineral water removed. The mass of montmorillonite and octadecanoic acid after mineral water removal was 99.82g and 100.2g, respectively. Other process conditions were the same as in Example 1.

[0050] Example 3

[0051] In the thermal simulation experiment, the temperature was increased to 330°C at a rate of 28°C / h, and the reaction was carried out at 330°C for 11 days. Other process conditions were the same as in Example 1.

[0052] Example 4

[0053] In the thermal simulation experiment, the temperature was increased to 350°C at a rate of 31°C / h, and the reaction was carried out at 350°C for 9 days. Other process conditions were the same as in Example 2.

[0054] Comparative Example 1 (System A: Blank - Octadecyl Acid)

[0055] The montmorillonite and glove box of Example 1 are omitted. Only 100.19g of octadecanoic acid is placed in the gold tube, and the other process conditions are the same as in Example 1.

[0056] Comparative Example 2 (System D: Montmorillonite-octadecanoic acid)

[0057] The montmorillonite dehydration step and glove box of Example 1 are omitted. 100.32g of octadecanoic acid and 100.39g of montmorillonite are directly mixed under natural conditions, and other process conditions are the same as in Example 1.

[0058] The effect of removing clay mineral water on organic matter pyrolysis was compared based on the gaseous hydrocarbon yield data of different systems A-D in Examples 1-2 and Comparative Examples 1-2. The gas collection volume in Examples 2-4 and Comparative Examples 1-2 was the same as in Example 1, which was 43 mL. The gaseous hydrocarbon yields in the four systems are shown in Table 1. Figures 3-7 As shown.

[0059] Table 1. Characteristics of gaseous products of system A-D under thermal simulation conditions of 340℃ and 10 days.

[0060] The yield of each gaseous hydrocarbon in Table 1 refers to the volume of each gas produced per gram of octadecanoic acid decomposition (volume under standard conditions).

[0061] The gas yields of different systems in Examples 1-2 and Comparative Examples 1-2 are as follows: Figure 3 As shown; the total gaseous hydrocarbon (∑C1-C5) yield and methane (C1) yield of different systems in Examples 1-2 and Comparative Examples 1-2 are as follows. Figure 4 As shown; the olefin / alkane ratios of different systems in Examples 1-2 and Comparative Examples 1-2 are, for example... Figure 5 As shown; the butane (C4) yield and butane / total gaseous hydrocarbon ratio (C4 / ∑C1-C5) of different systems in Examples 1-2 and Comparative Examples 1-2 are as follows. Figure 6 As shown; the isoalkane / n-alkane ratios of different systems in Examples 1-2 and Comparative Examples 1-2 are, for example... Figure 7 As shown, iC4 is isobutane, nC4 is n-butane, iC5 isopentane, and nC5 is n-pentane.

[0062] Under a unified reaction boundary and normalized evaluation caliber, comparisons were made using clay mineral water as the sole independent variable: when interlayer water (montmorillonite with adsorbed water removed) was dominant, the system's pyrolysis efficiency significantly improved, with the total hydrocarbon yield increasing from 9.295 mL·g in the blank group. -1 Compared with 30.818 mL·g of undehydrated MT -1 Increased to 60.651 mL·g -1 This is accompanied by an increase in the branched / normal ratio (e.g., the iC4 / nC4 ratio of montmorillonite-octadecanoic acid at 150℃ is 2.33, compared to 0.03 in the control group; the iC5 / nC5 ratio of montmorillonite-octadecanoic acid at 150℃ is 6.14, compared to 0.10 in the control group); montmorillonite without mineral water (montmorillonite-octadecanoic acid at 250℃) is more likely to show enhanced decarboxylation channels (e.g., CO2 is 26.022 mL·g). -1Based on this, the present invention establishes a verifiable experimental process of "endogenous water type - product spectrum characteristics - reaction channel", realizing a more scientific causal attribution and mechanism discrimination of the coupling effect of "water-mineral-organic matter". It can be directly extended to different clay minerals / model organic matter and temperature-time-ratio conditions, and can be orthogonally combined with factors such as exogenous water / acid and mineral type to carry out mechanism discrimination.

[0063] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for simulating the effect of montmorillonite clay mineral water on the pyrolysis of organic matter and hydrocarbon generation, characterized in that, It includes the following steps: 1) Montmorillonite was subjected to low-temperature heating and high-temperature heating respectively to obtain dehydrated montmorillonite: montmorillonite with adsorbed water removed and montmorillonite with mineral water removed; 2) Organic matter and dehydrated montmorillonite are mixed in an argon atmosphere and a dry environment to obtain a mixed sample, which is then transferred to a gold tube for loading. 3) Insert the gold tube into the iron reactor, fill the iron reactor with water, heat the reaction and then cool it; 4) After cooling, the gold tube is placed in a gas collection device, which is a glass collection device; the glass collection device is equipped with a puncture needle and a three-valve. After evacuating the gas collection device, record the gas pressure as P1; after the puncture needle pierces the gold tube and the reading stabilizes, record the gas pressure as P2; calculate the amount of substance of the gas based on the ideal gas law. The collected gases were analyzed by GC to obtain the percentage of each gas. The yield of each gas was calculated based on the amount of substance of the gas, and the impact of endogenous water in montmorillonite clay on the thermal decomposition of organic matter to generate hydrocarbons was evaluated.

2. The method according to claim 1, characterized in that, Step 1) The low-temperature heating temperature is 100~200℃, the high-temperature heating temperature is 200~300℃, and the low-temperature heating and high-temperature heating times are independent, each lasting 10~14 hours.

3. The method according to claim 1 or 2, characterized in that, Step 2) The humidity of the drying environment is ≤5%, and the purity of the organic matter is ≥98%; the organic matter contains octadecanoic acid.

4. The method according to claim 3, characterized in that, Step 2) The mass ratio of organic matter to dehydrated montmorillonite is 0.8~1.2:0.8~1.2; the mixing time is 17~23 min, and the mixing is carried out in a glove box.

5. The method according to claim 4, characterized in that, The gold tube has a length of 55-65 mm, a wall thickness of 0.2-0.3 mm, and an outer diameter of 5-7 mm; the iron reactor is equipped with a stopcock. Before loading the sample, one end of the gold tube is sealed with argon arc welding. After loading the sample, pinch the unsealed end of the gold tube and seal it in a cold water bath.

6. The method according to claim 4 or 5, characterized in that, Step 3) The heating reaction temperature is 330~350℃, the heating reaction time is 8~12 days, and the rate of heating to the heating reaction temperature is 28~32℃ / h.

7. The method according to claim 6, characterized in that, Step 4) Of the three valves in the glass collection device, one valve is connected to the vacuum pump, one valve is connected to the barometer, and one valve is connected to the collection bag.

8. The method according to claim 6, characterized in that, The ideal gas law is ΔPV = nRT, where ΔP = P2 - P1; V is the equivalent volume of the collection system; T is the temperature of the collected gas in K; R is a constant; and n is the amount of substance.

9. The method according to claim 7 or 8, characterized in that, The formula for calculating the gas yield is as follows: Where G is the gas yield (mL / g); n is the total amount of gas (mol); W is the percentage of this gas in the total gas (%); R is the volume of 1 mol of gas under standard conditions (22.4 L); and M is the mass of the reactants (mg).

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