Method for rapid industrial analysis on coal coke

Abstract

A method for rapid industrial analysis on coal coke, comprising the following steps: 1) setting a temperature control and atmosphere control system of a thermogravimetric analyzer in an industrial analysis process; and 2) putting an empty crucible into the thermogravimetric analyzer to perform a blank control experiment; and 3) weighing an experimental sample and loading same into the crucible; and 4) putting into the thermogravimetric analyzer the crucible containing the sample, and performing an experimental-group experiment; 5) performing data processing on experiment results, and automatically deducting the result of the blank control experiment to obtain a net thermogravimetric result of the sample; and 6) performing computational analysis on the composition of moisture, ash, volatile components and fixed carbon to obtain an industrial analysis result.

Description

A method for rapid industrial analysis of coal coke Technical Field

[0001] The invention belongs to the field of coal coke analysis, and in particular relates to a method for quickly performing industrial analysis on coal coke. Background Art

[0002] Existing analytical methods for the coke industry adhere to the national standard GB / T 2001-2013. The traditional test method involves weighing a certain amount of air-dried sample, placing it in a drying oven at 105-110°C, and drying it in a stream of air until the mass reaches a constant level. The moisture content is then calculated based on the mass loss. The volatile matter test method involves weighing a certain amount of air-dried sample, placing it in a covered porcelain crucible, and heating it at 900±10°C for 7 minutes, isolated from air. The volatile matter is calculated as the percentage of the sample mass lost, minus the calculated moisture content. The ash content test method (rapid ashing method) involves gradually transferring the sample-containing ash dish from outside the furnace into a muffle furnace preheated to 815±10°C for 1 hour. The ash content is calculated as the percentage of the sample mass. Due to the significant differences in the test conditions for ash and volatile matter, the tests for ash and volatile matter have always been conducted independently and one by one. The entire test process is time-consuming and inefficient, and cannot meet the requirements of rapid online analysis in industrial sites.

[0003] In the prior art, patent publication number CN1514226A discloses a non-continuous determination method and analyzer for industrial analysis of coal quality. The test furnace body is divided into a cylindrical furnace and a well-shaped furnace. The analyzer is equipped with a lifting sample delivery rod in the cylindrical furnace, and a lifting and rotating sample tray and an electronic balance for placing the sample crucible in the well-shaped furnace. The computer is connected to the lifting and rotating mechanism of the sample delivery rod and the sample tray and the electronic balance through a control circuit to control their movements, and is connected to the heating resistor and thermal coupler in the two furnaces to control the furnace temperature. The determination method is A coal sample crucible is placed on a sample tray and heated in a well-shaped furnace with nitrogen at 105-110°C until the mass is constant. The moisture percentage is automatically measured. The furnace is then heated to 815°C + / - 10°C with oxygen until the mass is constant. The ash yield is then calculated. A volatile matter crucible and coal sample are then placed in a cylindrical furnace heated at 900°C ± 10°C for 7 minutes to measure the volatile matter yield. This technical solution automatically completes the testing of four industrial analytical parameters for organic matter, such as coal and coke: moisture, ash, volatile matter, and fixed carbon. The testing process requires no human intervention, resulting in fast and efficient testing. However, this method requires a connected furnace, which compromises atmosphere control and makes switching between ash and volatile matter measurement zones more cumbersome.

[0004] Patent publication number CN101377483A discloses an industrial coal analysis method. This method simultaneously tests the ash and volatile content of air-dried coal samples in a single high-temperature furnace to determine the ash and volatile content values. The specific steps are: Before the test, the high-temperature furnace temperature is raised to 400-500°C and stabilized. After the ash-containing air-dried coal sample enters the high-temperature furnace, the temperature is raised at a prescribed rate of 20-30°C / min to 920±10°C and then held constant. The volatile-containing air-dried coal sample is placed in the high-temperature furnace undergoing the ash test. Due to the drop in temperature caused by the sample introduction, the high-temperature furnace temperature is restored to 900±10°C within 3 minutes and then held constant. After the volatile-containing air-dried coal sample is removed from the high-temperature furnace after the test, the furnace temperature is maintained at this temperature or lowered at a prescribed rate of 10-15°C / min to 815±10°C and held constant until the ash test is completed. The experiment also utilizes an automated analyzer, significantly reducing the total test time compared to traditional methods. However, the entire process from sample weighing, sample injection, heating, sample discharging to result weighing still consumes manpower and time, so it is necessary to find a faster and more accurate industrial analysis and testing method.

[0005] Summary of the Invention

[0006] The present invention aims to provide a method for rapid industrial analysis of coal char. Using a thermogravimetric analyzer (TGA), this method allows for more sensitive and accurate industrial analysis of organic carbon samples, such as coal or coke. The method analyzes the sample's moisture, ash, volatile matter, and fixed carbon composition by controlling temperature and the reaction atmosphere. This method shortens the overall experimental process, improves work efficiency, and reduces various errors caused by human manipulation. Furthermore, the experimental instrument is highly accurate and can meet the requirements of rapid industrial field analysis.

[0007] To achieve the above object, the present invention is implemented through the following technical solutions:

[0008] A method for rapidly performing industrial analysis on coal coke comprises the following steps:

[0009] 1) Set up temperature control and atmosphere control system for thermogravimetric analyzer during industrial analysis;

[0010] The temperature control system is as follows: heating to 105±5℃ at a rate of 10-20℃ / min, keeping warm for 10-15min, then heating to 900±5℃ at a rate of 10-20℃ / min, keeping warm at this temperature for 30-60min, then cooling to 815±5℃ at a rate of 10-20℃ / min, keeping warm at this temperature for 30-60min, then cooling to 25±5℃ at a rate of 10-20℃ / min;

[0011] The atmosphere control system is as follows: N2 is introduced at the beginning of the experiment, and the gas flow rate is set to 60-100 ml / min. When the temperature drops to 815±10℃, the gas is replaced with air, and the gas flow rate is still 60-100 ml / min. After the end of the 815±10℃ holding period, the gas is replaced with N2.

[0012] 2) Place the empty crucible into the thermogravimetric analyzer to perform a blank control experiment;

[0013] 3) Weigh the experimental sample and place it into a crucible;

[0014] 4) Place the crucible containing the sample into the thermogravimetric analyzer to conduct the experimental group experiment;

[0015] 5) Perform data processing on the experimental results, automatically deduct the results of the blank control experiment, and obtain the net thermogravimetric analysis results of the samples;

[0016] 6) Calculate and analyze the moisture, ash, volatile matter, and fixed carbon composition to obtain industrial analysis results.

[0017] The material of the crucible is Al2O3 crucible.

[0018] The experimental sample is organic carbon, and the particle size of the experimental sample is 100-400 μm.

[0019] The organic carbon material is coal and / or coke.

[0020] Step 4) Record the net content of the sample before the experiment; and conduct the experiment according to the temperature control and atmosphere control system set in step 1).

[0021] The temperature control and atmosphere control system used in step 4) are the same as those in step 1).

[0022] In step 5), the data of the experimental group are background-subtracted based on the results of the blank control group to obtain the thermogravimetric curve of the experimental sample.

[0023] Calculation process in step 6):

[0024] After the experiment begins, the temperature is raised to 105±5℃ in the first stage and kept warm for 10-15 minutes. This stage is the water loss stage. After the weight loss stabilizes, the relative proportion of water M is calculated:

[0025] In formula (1), m1 is the mass of the experimental sample recorded before the start of the experiment, unit: g; m2 is the mass of the experimental sample recorded after the weightlessness is stabilized in the first stage, unit: g;

[0026] The second stage is to heat up to 900±5℃ and keep it warm for 30~60min. This stage is the pyrolysis stage of volatile matter. After the weight loss stabilizes, the relative proportion of volatile matter V is calculated:

[0027] In formula (2), m3 is the mass of the experimental sample recorded after the weightlessness is stabilized in the second stage, unit: g;

[0028] The third stage is to cool down to 815±5℃ and keep warm for 30~60min. This stage is the combustion stage of fixed carbon in air environment. After the weight loss stabilizes, the relative proportion of fixed carbon C is calculated:

[0029] In formula (3), m4 is the mass of the experimental sample recorded after the weightlessness is stabilized in the third stage, unit: g;

[0030] After the experiment is completed, calculate the relative proportion of ash A:

[0031] In formula (4), m5 is the mass of the remaining solid sample recorded after the experiment is completed, unit: g.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The method of the present invention enables rapid industrial analysis of carbonaceous organic materials such as coal, coke, and biomass, allowing for repeated experiments in a short time. The thermogravimetric analyzer provides more accurate mass detection, the balance has higher sensitivity, and temperature control is more precise, with smaller errors, thus improving the credibility of the results. Simultaneously, it significantly saves manpower and material resources, greatly reducing the cost of industrial analysis (such as energy consumption of crucibles and high-temperature muffle furnaces). This method is particularly useful for simultaneous comparison of large batches of samples.

[0034] The method of the present invention can shorten the time of the entire experimental process, greatly improve work efficiency, and reduce various errors caused by human operation. In addition, the experimental instrument is highly accurate and can meet the requirements of rapid analysis on industrial sites. The calculation parameters are all obtained by the instrument, reducing the errors caused by human operation, laying a foundation for the evaluation of coke. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is a schematic diagram of the temperature system setting and atmosphere control setting.

[0036] FIG2 is a quick industrial analysis diagram of the metallurgical coke powder of Example 1.

[0037] FIG3 is a quick industrial analysis diagram of the coal powder of Example 2.

[0038] FIG4 is a diagram of rapid industrial analysis of biomass in Example 3. DETAILED DESCRIPTION

[0039] The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the implementation of the present invention is not limited to the following embodiments.

[0040] See Figure 1 for a method for rapid industrial analysis of coal coke. The specific steps are as follows:

[0041] 1. The temperature control system during the process is as follows: after the program starts, heat up to 105±5℃ at a rate of 10~20℃ / min, keep warm for 10~15min, then continue to heat up to 900±5℃ at a rate of 10~20℃ / min, keep warm at this temperature for 30~60min, then cool down to 815±3℃ at a rate of 10~20℃ / min, keep warm at this temperature for 30~60min, then cool down to 25±5℃ at a rate of 10~20℃ / min

[0042] 2. The atmosphere during the process was set as follows: N2 was introduced at the beginning of the experiment, and the gas flow rate was set to 60-100 ml / min. When the temperature dropped to 815°C, the gas was replaced with air, and the gas flow rate remained at 60-100 ml / min. After the 815°C insulation was completed, the gas was replaced with N2.

[0043] 3. Blank control group: Use blank Al2O3 crucible to conduct blank control experiment.

[0044] 4. Experimental group: Dry the experimental sample (organic carbon) in air and crush it to 100-400 μm. Weigh 5-15 mg of the powdered sample and place it in the Al2O3 crucible used in the blank group. The sample amount should not exceed 2 / 3 of the crucible volume. While ensuring that the sample can be spread flat on the bottom of the crucible, try to reduce the sample amount so that the sample can be spread flat on the bottom of the crucible. Place the crucible with the sample on the thermogravimetric analyzer.

[0045] 5. Select the same temperature and atmosphere system as the blank sample, and conduct the experiment on the experimental group according to the prescribed operation.

[0046] 6. After the experiment, the data of the experimental group will be background subtracted based on the results of the blank control group.

[0047] 7. Calculation process: After the experiment starts, the first stage is the water loss stage. After the weight loss stabilizes, the relative proportion of water is calculated; the second stage is the pyrolysis stage of volatile matter. After the weight loss stabilizes, the relative proportion of volatile matter is calculated; the third stage is the combustion stage of fixed carbon in an air environment. After the weight loss stabilizes, the relative proportion of fixed carbon is calculated; the remaining solid amount after the experiment is completed is the relative proportion of ash.

[0048] Example 1:

[0049] Thermogravimetric analyzer is used to perform industrial analysis on metallurgical coke powder from coking enterprises. The specific operations are as follows:

[0050] 1. Set the temperature control system and atmosphere control system of the thermogravimetric analyzer:

[0051] The temperature regime during the process was as follows: after the program started, the temperature was raised to 105°C at a rate of 15°C / min, kept at this temperature for 10 minutes, then continued to be raised to 900°C at a rate of 15°C / min, and kept at this temperature for 30 minutes, then cooled to 815°C at a rate of 15°C / min, and kept at this temperature for 30 minutes, and then cooled to 25°C at a rate of 15°C / min.

[0052] The atmosphere during the process was set as follows: N2 was introduced in advance at the beginning of the experiment, and the gas flow rate was set to 60 ml / min. When the temperature dropped to 815°C, the gas was replaced with air, and the gas flow rate was still 60 ml / min. After the 815°C insulation was completed, the gas was replaced with N2.

[0053] 2. Blank control group: Select a blank Al2O3 crucible with a certain volume for blank control experiment.

[0054] 3. Experimental group: The coke was dried in air and crushed to 200 μm. 10 mg of powdered sample was weighed and placed in the Al2O3 crucible used in the blank group. The sample amount did not exceed 2 / 3 of the crucible volume. The sample was spread flat on the bottom of the crucible. The crucible filled with the sample was placed on the thermogravimetric analyzer.

[0055] 4. Select the same temperature control system and atmosphere control system as the blank sample. Before the experiment begins, it is necessary to record the net content of the sample as 10.85 mg and conduct the experiment according to the prescribed operation.

[0056] 5. After the experiment, the data of the experimental group were background subtracted based on the results of the blank control group to obtain the results shown in Figure 2.

[0057] 6. Calculation process: By extracting and calculating the data at different stages, the final calculation results (by mass percentage) are: moisture 1.84%, ash 13.18%, volatile matter 5.6%, and fixed carbon 79.35%.

[0058] Example 2:

[0059] Thermogravimetric analyzer is used to conduct industrial analysis and testing on a single type of pulverized coal. The specific operations are as follows:

[0060] 1. Set the temperature system and atmosphere control system of the thermogravimetric analyzer

[0061] The temperature regime during the process was as follows: after the program started, the temperature was raised to 105°C at a rate of 15°C / min, kept at this temperature for 10 minutes, then continued to be raised to 900°C at a rate of 15°C / min, and kept at this temperature for 30 minutes, then cooled to 815°C at a rate of 15°C / min, and kept at this temperature for 30 minutes, and then cooled to 25°C at a rate of 15°C / min.

[0062] The atmosphere during the process was set as follows: N2 was introduced in advance at the beginning of the experiment, and the gas flow rate was set to 60 ml / min. When the temperature dropped to 815°C, the gas was replaced with air, and the gas flow rate was still 60 ml / min. After the 815°C insulation was completed, the gas was replaced with N2.

[0063] 2. Blank control group: Select a blank Al2O3 crucible with a certain volume for blank control experiment.

[0064] 3. Experimental group: Dry the coke in air and crush it to 200 μm. Weigh about 5 mg of powdered sample and place it in the Al2O3 crucible used in the blank group. The sample amount should not exceed 2 / 3 of the crucible to ensure that the sample can be spread flat on the bottom of the crucible. Place the crucible filled with the sample on the thermogravimetric analyzer.

[0065] 4. Select the same temperature control system and atmosphere control system as the blank sample. Before the experiment begins, it is necessary to record the net content of the sample as 6.16 mg and conduct the experiment according to the prescribed operation.

[0066] 5. After the experiment, the data of the experimental group were background subtracted based on the results of the blank control group to obtain the results shown in Figure 3.

[0067] 6. Calculation process: By extracting and calculating the data at different stages, the final calculation results (by mass percentage) are: moisture 1.14%, ash 8.45%, volatile matter 19.67%, and fixed carbon 70.73%.

[0068] Example 3:

[0069] Thermogravimetric analyzer was used to conduct industrial analysis and testing on a single hydrothermal treated biochar. The specific operation was as follows:

[0070] 1. Set the temperature system and atmosphere control system of the thermogravimetric analyzer

[0071] The temperature regime during the process was as follows: after the program started, the temperature was raised to 105°C at a rate of 15°C / min, kept at this temperature for 10 minutes, then continued to be raised to 900°C at a rate of 15°C / min, and kept at this temperature for 30 minutes, then cooled to 815°C at a rate of 15°C / min, and kept at this temperature for 30 minutes, and then cooled to 25°C at a rate of 15°C / min.

[0072] The atmosphere during the process was set as follows: N2 was introduced in advance at the beginning of the experiment, and the gas flow rate was set to 60 ml / min. When the temperature dropped to 815°C, the gas was replaced with air, and the gas flow rate was still 60 ml / min. After the 815°C insulation was completed, the gas was replaced with N2.

[0073] 2. Blank control group: Select a blank Al2O3 crucible with a certain volume for blank control experiment.

[0074] 3. Experimental group: The biochar was dried in air and crushed to 200 μm. About 6 mg of powdered sample was weighed and placed in the Al2O3 crucible used in the blank group. The sample amount did not exceed 2 / 3 of the crucible volume to ensure that the sample could be spread flat on the bottom of the crucible. The crucible filled with the sample was placed on the thermogravimetric analyzer.

[0075] 4. Select the same temperature and atmosphere system as the blank sample. Before the experiment begins, record the net content of the sample as 6.35 mg and conduct the experiment according to the specified operation.

[0076] 5. After the experiment, the data of the experimental group were background subtracted based on the results of the blank control group, and the results shown in Figure 3 were obtained.

[0077] 6. Calculation process: By extracting and calculating the data at different stages, the final calculation results (by mass percentage) are: moisture 1.11%, ash 2.68%, volatile matter 43.00%, and fixed carbon 52.22%.

Claims

1. A method for rapid industrial analysis of coal coke, characterized in that: The following steps are involved: 1) Set up the temperature control and atmosphere control system of thermogravimetric analyzer during industrial analysis; The temperature control system is as follows: heating to 105±5℃ at a rate of 10~20℃ / min, keeping at that temperature for 10~15min, then heating to 900±5℃ at a rate of 10~20℃ / min, keeping at that temperature for 30~60min, then cooling to 815±5℃ at a rate of 10~20℃ / min, keeping at that temperature for 30~60min, then cooling to 25±5℃ at a rate of 10~20℃ / min; The atmosphere control system is as follows: N2 is introduced at the beginning of the experiment, and the gas flow rate is set to 60-100 ml / min. When the temperature drops to 815±10℃, the gas is replaced with air, and the gas flow rate remains at 60-100 ml / min. After the 815±10℃ insulation is completed, the gas is replaced with N2. 2) Place the empty crucible into the thermogravimetric analyzer to perform a blank control experiment; 3) Weigh the experimental sample and put it into the crucible; 4) Place the crucible containing the sample into a thermogravimetric analyzer to conduct the experimental group experiment; 5) Performing data processing on the experimental results, automatically deducting the results of the blank control experiment, and obtaining the net thermogravimetric analysis results of the samples; 6) Calculate and analyze the moisture, ash, volatile matter and fixed carbon composition to obtain industrial analysis results.

2. A method for rapid industrial analysis of coal char according to claim 1, characterized in that: The material of the crucible is Al2O3 crucible.

3. A method for rapid industrial analysis of coal char according to claim 1, characterized in that: The experimental sample is organic carbon, and the particle size of the experimental sample is 100-400 μm.

4. A method for rapid industrial analysis of coal char according to claim 3, characterized in that: The organic carbon material is coal and / or coke.

5. The method for rapid industrial analysis of coal char according to claim 1, characterized in that: Step 4) Record the net content of the sample before the experiment; and conduct the experiment according to the temperature control and atmosphere control system set in step 1).

6. A method for rapid industrial analysis of coal char according to claim 1, characterized in that: The temperature control and atmosphere control system used in step 4) are the same as those in step 1).

7. A method for rapid industrial analysis of coal char according to claim 1, characterized in that: In step 5), the data of the experimental group are background-subtracted based on the results of the blank control group to obtain the thermal gravimetric curve of the experimental sample.

8. A method for rapid industrial analysis of coal char according to claim 1, characterized in that: The calculation process in step 6) is: After the experiment started, the temperature was raised to 105±5℃ in the first stage and kept warm for 10-15min. This stage was the water loss stage. After the weight loss stabilized, the relative proportion of water M was calculated: In formula (1), m1 is the mass of the experimental sample recorded before the experiment, unit: g; m2 is the mass of the experimental sample recorded after weightlessness is stabilized in the first stage, unit: g; The second stage is to heat up to 900±5℃ and keep warm for 30-60min. This stage is the pyrolysis stage of volatiles. After the weight loss is stable, the relative proportion V of volatiles is calculated: In formula (2), m3 is the mass of the experimental sample recorded after the weightlessness is stabilized in the second stage, unit: g; The third stage is cooling to 815±5℃ and keeping warm for 30-60min. This stage is the combustion stage of fixed carbon in air environment. After the weight loss is stable, the relative proportion C of fixed carbon is calculated: In formula (3), m4 is the mass of the experimental sample recorded after the weightlessness is stabilized in the third stage, unit: g; After the experiment is completed, calculate the relative proportion of ash A: In formula (4), m5 is the mass of the remaining solid sample recorded after the experiment is completed, unit: g.

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