A method for rapidly performing industrial analysis of coal and coke.

Abstract

The present invention relates to a method for rapidly performing industrial analysis of coal and coke, which includes the steps of: 1) setting temperature and atmosphere control levels in the industrial analysis process using a thermogravimetric analyzer; 2) placing an empty crucible in the thermogravimetric analyzer to conduct a blank control experiment; 3) weighing the experimental sample and loading it into the crucible; 4) placing the crucible containing the sample in the thermogravimetric analyzer to conduct experiments for the experimental group; 5) processing the experimental results and automatically subtracting the results of the blank control experiment to obtain the thermogravimetric analysis results for the sample itself; and 6) calculating and analyzing the contents of moisture, ash, volatile matter, and fixed carbon to obtain the industrial analysis results. This method has the advantages of enabling rapid industrial analysis of organic carbon materials such as coal, coke, and biomass, allowing repeated experiments to be performed in a short period of time, and achieving more reliable results due to more accurate mass measurement by the thermogravimetric analyzer, higher sensitivity of the balance, more accurate temperature control, and smaller error.

Description

Technical Field

[0001] The present invention relates to the field of coal and coke analysis, and particularly to a method for quickly performing industrial analysis of coal and coke.

Background Art

[0002] The specific procedures of the Chinese national standard GB / T2001 - 2013 used in the conventional coke industrial analysis measurement method are as follows. In the conventional measurement method, a predetermined amount of air-dried sample is weighed and placed in a dryer at 105 - 110°C, and after drying in an air stream until the mass becomes constant, the moisture content (%) is calculated from the mass reduction of the coal sample. The test method for volatile matter is to weigh a predetermined amount of air-dried sample, put it into a ceramic crucible with a lid, heat it at 900 ± 10°C for 7 min in a state of blocking air, and from the ratio (%) of the reduced mass to the mass of the coal sample, the value obtained by subtracting the moisture content calculated from the coal sample is taken as the volatile matter of the coal sample. The test method for ash content (rapid ashing method) is to gradually send the ash pan containing the sample into a muffler furnace preheated to 815 ± 10°C from outside the furnace and bake it for 1 h, and the ratio (%) of the mass of the residue to the mass of the coal sample is taken as the ash content. Since the test conditions for ash content and volatile matter are very different, usually, the tests for ash content and volatile matter are carried out independently and sequentially, and the whole test takes a long time, the working efficiency is low, and it cannot meet the requirement of rapid on-line analysis in the industrial field.

[0003] Among the prior art, patent publication number CN1514226A discloses a discontinuous measurement method and analytical apparatus for industrial analysis of coal-based materials. The test furnace is divided into a cylindrical furnace and a well-shaped furnace. In the analytical apparatus, a vertically movable sample supply rod is built into the cylindrical furnace, and a vertically movable and rotatable sample mounting platform for placing a sample crucible and an electronic balance are built into the well-shaped furnace. A computer is connected to the sample supply rod, the vertical and rotatable mechanism of the sample mounting platform and the electronic balance via a control circuit to control their operation, and is also connected to the heating resistors and thermocouples in both furnaces to control the furnace temperature. In the measurement method, a coal sample crucible is placed on a sample stand, and while nitrogen gas is flowed into a well-shaped furnace, it is heated at 105-110°C until the mass becomes constant, and the moisture content (%) is automatically calculated. Then, the gas is switched to oxygen, and it is heated at 815°C + 10°C until the mass becomes constant, and the ash content is calculated. Next, the volatile matter measurement crucible and coal sample are loaded and moved into a cylindrical furnace at 900°C ± 10°C, heated for 7 minutes, and the volatile matter content is measured. This technical means allows for the automatic measurement of four industrial analytical indicators of organic materials such as coal and coke: moisture, ash content, volatile matter, and fixed carbon. The measurement process does not require monitoring, is fast, and is highly efficient. However, in this method, the furnace bodies are connected, making it difficult to ensure atmosphere control, and the measurement areas for ash content and volatile matter are swapped, which can be unnecessarily complicated.

[0004] Patent publication number CN101377483A discloses an industrial analysis method for coal in which ash content and volatile matter are simultaneously measured in an air-dried coal sample in the same high-temperature furnace to obtain ash content and volatile matter values. The specific steps are as follows: Before the test, the temperature of the high-temperature furnace is raised to 400-500°C and maintained therein. An air-dried coal sample for ash content measurement is loaded into the high-temperature furnace and raised to 920±10°C at a predetermined rate of 20-30°C / min and maintained therein. An air-dried coal sample for volatile matter measurement is loaded into the high-temperature furnace in which the ash content test is being conducted. The temperature of the high-temperature furnace, which was lowered by loading the sample, is returned to 900±10°C within 3 minutes and maintained therein. After the test of the air-dried coal sample for volatile matter measurement is completed and it is removed from the high-temperature furnace, the furnace temperature at this time is maintained, or the temperature of the high-temperature furnace is lowered to 815±10°C at a predetermined rate of 10-15°C / min and maintained therein until the ash content test is completed. The experiment utilizes automated analyzers, significantly reducing the total testing time compared to conventional methods. However, all processes, from sample weighing, loading, heating, and removal to post-test weighing, still require manual labor and time, highlighting the need for faster and more accurate industrial analytical measurement methods. [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a method for rapidly performing industrial analysis of coal and coke. By using a thermogravimetric analyzer (TGA), it enables more sensitive and accurate industrial analysis of organic carbon samples such as coal and coke. By controlling temperature changes and reaction atmospheres during the process, it analyzes the moisture, ash, volatile matter, and fixed carbon content of the sample, shortening the overall experimental time, improving work efficiency, reducing various errors caused by human error, and the highly accurate experimental equipment can meet the rapid analysis demands of industrial sites. [Means for solving the problem]

[0006] To achieve the above objective, the present invention employs the following technical means. A method for performing rapid industrial analysis of coal and coke, including the steps outlined below. 1) Steps to establish temperature control and atmosphere control systems in industrial analysis processes using thermogravimetric analyzers; Temperature control procedure: The temperature is raised to 105±5℃ at a rate of 10-20℃ / min and maintained at this temperature for 10-15 minutes, then raised to 900±5℃ at a rate of 10-20℃ / min and maintained at this temperature for 30-60 minutes, then cooled to 815±5℃ at a rate of 10-20℃ / min and maintained at this temperature for 30-60 minutes, then cooled to 25±5℃ at a rate of 10-20℃ / min; Atmosphere control system: At the start of the experiment, nitrogen is initially supplied to maintain a gas flow rate of 60-100 ml / min. When the temperature drops to 815±10℃, the gas is switched to air, maintaining the same flow rate of 60-100 ml / min. After maintaining the temperature at 815±10℃, the gas is switched back to nitrogen. 2) A blank control experiment is performed by placing an empty crucible into a thermogravimetric analyzer; 3) Weighing the experimental sample and loading it into the crucible; 4) The step of placing the crucible containing the sample into a thermogravimetric analyzer and conducting the experiment on the experimental group; 5) A step of processing the experimental results, automatically subtracting the results of the blank control experiment to obtain the thermogravimetric analysis results of the sample itself; and 6) A step to obtain the results of industrial analysis by calculating and analyzing the content of moisture, ash, volatile matter, and fixed carbon.

[0007] The aforementioned crucible is a crucible made of Al2O3. The experimental sample is an organic carbonaceous material, and its particle size is 100 to 400 μm. The organic carbonaceous material is coal and / or coke. For step 4), record the net mass of the sample before conducting the experiment, and perform the experiment according to the temperature control precision and atmosphere control precision set in step 1). The temperature control system and atmosphere control system used in Step 4) are the same as those used in Step 1). In step 5), the experimental group data is baseline-corrected based on the results of the blank control group to obtain the thermogravimetric loss curve of the experimental sample.

[0008] The calculation in step 6) is as follows: In the first stage of the dehydration phase, after the start of the experiment, the temperature is raised to 105±5℃ and maintained at this temperature for 10-15 minutes. Once the weight loss stabilizes, the relative percentage of water, M, is calculated;

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[0009] In the second stage, which involves heating to 900±5℃ and maintaining the temperature for 30-60 minutes to decompose volatile components, once the weight loss stabilizes, the relative proportion V of volatile components is calculated;

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[0010] In the third stage, which is the combustion phase of fixed carbon under an air atmosphere cooled to 815±5℃ and maintained for 30-60 minutes, once the weight loss stabilizes, the relative proportion C of fixed carbon is calculated;

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[0011] After the experiment is completed, calculate the relative proportion A of the ash content.

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[0012] Compared to the prior art, the present invention offers the following beneficial effects. The method of the present invention can quickly perform industrial analysis of organic carbon materials such as coal, coke, and biomass, can repeatedly conduct experiments in a short time, enables more accurate mass measurement by a thermogravimetric analyzer, has higher balance sensitivity, more accurate temperature control, and smaller errors, thus improving the reliability of results. Also, to greatly save human and material resources, it significantly reduces the measurement costs of industrial analysis (such as crucibles, energy consumption of high-temperature muffles, etc.). In particular, it is suitable for simultaneously measuring and comparing a large number of samples.

[0013] The method of the present invention can shorten the total time of the experiment, thus greatly improving work efficiency, reducing various errors caused by manual operations, and moreover, the experimental equipment is highly accurate and can meet the rapid analysis requirements in industrial sites. Since all calculation parameters are obtained by the equipment, it reduces errors caused by manual operations and establishes a basis for the evaluation of coke.

Brief Description of the Drawings

[0014] [Figure 1] It is a schematic diagram of temperature regime setting and atmosphere regime setting. [Figure 2] It is a diagram for quickly performing industrial analysis of metallurgical pulverized coke in Example 1. [Figure 3] It is a diagram for quickly performing industrial analysis of coal powder in Example 2. [Figure 4] It is a diagram for quickly performing industrial analysis of biomass in Example 3.

Embodiments for Carrying Out the Invention

[0015] Hereinafter, the present invention will be described in detail with reference to the drawings, but it should be pointed out that the implementation of the present invention is not limited to the following embodiments. As shown in FIG. 1, the method for quickly performing industrial analysis of coal and coke is specifically carried out according to the following procedure. 1. Temperature control precision in the process: After the program starts, the temperature is raised to 105±5℃ at a rate of 10-20℃ / min and maintained at this temperature for 10-15 minutes, then raised to 900±5℃ at a rate of 10-20℃ / min and maintained at this temperature for 30-60 minutes, then cooled to 815±3℃ at a rate of 10-20℃ / min and maintained at this temperature for 30-60 minutes, then cooled to 25±5℃ at a rate of 10-20℃ / min. 2. Setting the atmosphere in the process: At the start of the experiment, nitrogen is initially flowed to set the gas flow rate to 60-100 ml / min. When the temperature drops to 815°C, the gas is switched to air and the gas flow rate is set to the same rate of 60-100 ml / min. After the temperature is maintained at 815°C, the gas is switched back to nitrogen. 3. Blank control group: A blank control experiment is performed using an empty Al2O3 crucible. 4. Experimental group: The experimental sample (organic carbonaceous material) was dried in air and crushed to 100-400 μm. 5-15 mg of the sample powder was weighed and placed into the Al2O3 crucible used for the blank control group, ensuring that the sample volume did not exceed 2 / 3 of the crucible volume and that the sample spread to the bottom of the crucible (minimizing the sample volume while ensuring the sample spreads to the bottom of the crucible). The crucible containing the sample was then placed in a thermogravimetric analyzer. 5. The experiment with the experimental group will be conducted according to the prescribed procedure, using the same temperature and atmosphere control as the blank control group. 6. After the experiment is completed, the experimental group's data will be baseline-corrected based on the results of the blank control group. 7. Calculation process: After the start of the experiment, the first stage is the dehydration stage, and once the weight loss stabilizes, the relative proportion of water is calculated; the second stage is the thermal decomposition stage of volatile components, and once the weight loss stabilizes, the relative proportion of volatile components is calculated; the third stage is the combustion stage of fixed carbon under an air atmosphere, and once the weight loss stabilizes, the relative proportion of fixed carbon is calculated; and after the experiment is completed, the relative proportion of ash is calculated from the amount of solid remaining. [Examples]

[0016] Example 1 An industrial analysis of metallurgical coke powder from a coke manufacturing plant was conducted using a thermogravimetric analyzer, and the specific procedure was as follows. 1. Setting the temperature control and atmosphere control standards for the thermogravimetric analyzer. Temperature control in the process: After the program started, the temperature was raised to 105°C at a rate of 15°C / min and held at this temperature for 10 minutes, then raised to 900°C at a rate of 15°C / min and held at this temperature for 30 minutes, then cooled to 815°C at a rate of 15°C / min and held at this temperature for 30 minutes, and then cooled to 25°C at a rate of 15°C / min. Atmosphere setting during the process: At the start of the experiment, nitrogen was initially flowed to set the gas flow rate to 60 ml / min. When the temperature dropped to 815°C, the gas was switched to air and the gas flow rate was maintained at the same rate of 60 ml / min. After the temperature was maintained at 815°C, the gas was switched back to nitrogen. 2. Blank control group: A blank control experiment was conducted using an empty Al2O3 crucible of a predetermined volume. 3. Experimental group: Coke was dried in air and crushed to 200 μm. 10 mg of the sample powder was weighed and placed in the Al2O3 crucible used for the blank control group, ensuring the sample volume did not exceed 2 / 3 of the crucible volume and that the sample was spread to the bottom of the crucible. The crucible containing the sample was then placed in a thermogravimetric analyzer. 4. Using the same temperature and atmosphere control systems as the blank control group, the net mass of the sample (10.85 mg) was recorded before the start of the experiment, and the experiment was conducted according to the prescribed procedure. 5. After the experiment was completed, the experimental group data was baseline-corrected based on the results of the blank control group, and the results shown in Figure 2 were obtained. 6. Calculation process: After extracting and calculating data for each stage, the mass percentages were found to be 1.84% water, 13.18% ash, 5.6% volatile matter, and 79.35% fixed carbon.

[0017] Example 2 Industrial analysis of coal powder was performed using a thermogravimetric analyzer, and the specific procedure was as follows. 1. Setting the temperature control and atmosphere control standards for the thermogravimetric analyzer. Temperature control in the process: After the program started, the temperature was raised to 105°C at a rate of 15°C / min and held at this temperature for 10 minutes, then raised to 900°C at a rate of 15°C / min and held at this temperature for 30 minutes, then cooled to 815°C at a rate of 15°C / min and held at this temperature for 30 minutes, and then cooled to 25°C at a rate of 15°C / min. Atmosphere setting during the process: At the start of the experiment, nitrogen was initially flowed to set the gas flow rate to 60 ml / min. When the temperature dropped to 815°C, the gas was switched to air and the gas flow rate was maintained at the same rate of 60 ml / min. After the temperature was maintained at 815°C, the gas was switched back to nitrogen. 2. Blank control group: A blank control experiment was conducted using an empty Al2O3 crucible of a predetermined volume. 3. Experimental group: Coke was dried in air and crushed to 200 μm. Approximately 5 mg of the sample powder was weighed and placed in the Al2O3 crucible used for the blank control group, ensuring that the sample volume did not exceed 2 / 3 of the crucible volume and that the sample was spread out at the bottom of the crucible. The crucible containing the sample was then placed in a thermogravimetric analyzer. 4. Using the same temperature and atmosphere control systems as the blank control group, the net mass of the sample (6.16 mg) was recorded before the start of the experiment, and the experiment was conducted according to the prescribed procedure. 5. After the experiment was completed, the experimental group data was baseline-corrected based on the results of the blank control group, and the results shown in Figure 3 were obtained. 6. Calculation process: After extracting and calculating the data for each stage, the mass percentages were found to be 1.14% water, 8.45% ash, 19.67% volatile matter, and 70.73% fixed carbon.

[0018] Example 3 Industrial analysis of biomass char treated by the hydrothermal method was performed using a thermogravimetric analyzer, and the specific procedure was as follows. 1. Setting the temperature control and atmosphere control standards for the thermogravimetric analyzer. Temperature control in the process: After the program started, the temperature was raised to 105°C at a rate of 15°C / min and held at this temperature for 10 minutes, then raised to 900°C at a rate of 15°C / min and held at this temperature for 30 minutes, then cooled to 815°C at a rate of 15°C / min and held at this temperature for 30 minutes, and then cooled to 25°C at a rate of 15°C / min. Atmosphere setting during the process: At the start of the experiment, nitrogen was initially flowed to set the gas flow rate to 60 ml / min. When the temperature dropped to 815°C, the gas was switched to air and the gas flow rate was maintained at the same rate of 60 ml / min. After the temperature was maintained at 815°C, the gas was switched back to nitrogen. 2. Blank control group: A blank control experiment was conducted using an empty Al2O3 crucible of a predetermined volume. 3. Experimental group: Biomass charcoal was dried in air and crushed to 200 μm. Approximately 6 mg of the sample powder was weighed and placed in the Al2O3 crucible used for the blank control group, ensuring that the sample volume did not exceed 2 / 3 of the crucible volume and that the sample was spread out at the bottom of the crucible. The crucible containing the sample was then placed in a thermogravimetric analyzer. 4. Using the same temperature and atmosphere control systems as the blank control group, the net mass of the sample (6.35 mg) was recorded before the start of the experiment, and the experiment was conducted according to the prescribed procedure. 5. After the experiment was completed, the experimental group data was baseline-corrected based on the results of the blank control group, and the results shown in Figure 4 were obtained. 6. Calculation process: After extracting and calculating the data for each stage, the mass percentages were found to be 1.11% water, 2.68% ash, 43.00% volatile matter, and 52.22% fixed carbon.

Claims

1. A method for rapidly performing industrial analysis of organic carbonaceous materials, characterized by including the following steps. 1) Steps to establish temperature control and atmosphere control systems in industrial analysis processes using thermogravimetric analyzers; Temperature control precision: The temperature is raised to 105±5°C at a rate of 10-20°C / min and maintained at this temperature for 10-15 minutes, then raised to 900±5°C at a rate of 10-20°C / min and maintained at this temperature for 30-60 minutes, then cooled to 815±5°C at a rate of 10-20°C / min and maintained at this temperature for 30-60 minutes, then cooled to 25±5°C at a rate of 10-20°C / min; Atmosphere control system: At the start of the experiment, nitrogen is initially supplied to maintain a gas flow rate of 60-100 ml / min. When the temperature drops to 815±5°C, the gas is switched to air, maintaining the same flow rate of 60-100 ml / min. Once the temperature is maintained at 815±5°C, the gas is switched back to nitrogen. 2) Place an empty crucible into the thermogravimetric analyzer and perform a blank control experiment according to the temperature control and atmosphere control settings set in step 1); 3) Weighing the experimental sample and loading it into the crucible; 4) The crucible containing the sample is placed in a thermogravimetric analyzer, and the experimental group is subjected to the same temperature and atmosphere control precision as in the blank control experiment; 5) A step of processing the experimental results, automatically subtracting the results of the blank control experiment to obtain the thermogravimetric analysis results of the sample itself; and 6) A step to obtain the results of industrial analysis by calculating and analyzing the content of moisture, ash, volatile matter, and fixed carbon.

2. The aforementioned crucible is made of Al ２ O ３ A method for rapidly performing industrial analysis of organic carbonaceous materials according to claim 1, characterized in that it is a crucible.

3. The method for rapidly performing industrial analysis of organic carbonaceous materials according to Claim 1, characterized in that the particle size of the experimental sample is 100 to 400 μm.

4. The method for rapidly performing industrial analysis of organic carbonaceous material according to claim 1, characterized in that the organic carbonaceous material is selected from coal, coke, and biomass coal.

5. Step 5) is characterized by obtaining a thermogravimetric loss curve of the experimental sample by baseline correction of the experimental group data based on the results of the blank control group. This is a method for rapidly performing industrial analysis of organic carbonaceous materials according to claim 1.

6. The method for rapidly performing industrial analysis of organic carbonaceous materials according to claim 1, characterized in that the calculation in step 6) is as follows. In the first stage of the dehydration phase, after the start of the experiment, the temperature is raised to 105±5°C and maintained at this temperature for 10-15 minutes. Once the weight loss stabilizes, the relative percentage M of water is calculated; [Math 1] [In formula (1), m １ (Unit: g) is the mass of the experimental sample recorded before the start of the experiment, m ２ (Unit: g) represents the mass of the experimental sample recorded when the weight loss stabilized in the first stage. In the second stage, which involves heating to 900±5℃ and maintaining the temperature for 30-60 minutes to decompose the volatile components, once the weight loss stabilizes, the relative proportion V of the volatile components is calculated; [Math 2] [In formula (2), m ３ (Unit: g) represents the mass of the experimental sample recorded when the weight loss stabilized in the second stage. In the third stage, which is the combustion phase of fixed carbon under an air atmosphere cooled to 815±5℃ and maintained for 30-60 minutes, once the weight loss stabilizes, the relative proportion C of fixed carbon is calculated; [Math 3] [In formula (3), m ４ (Unit: g) represents the mass of the experimental sample recorded when the weight loss stabilized in the third stage. After the experiment is completed, calculate the relative proportion A of the ash content. [Math 4] [In formula (4), m ５ (Unit: g) represents the mass of residual solid recorded after the experiment.

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