HG/T 2780-1996 Test method for sulfur-tolerant carbon monoxide shift catalyst
Some standard content:
HG/T2780—1996
This standard is matched with the standard of "Carbon Monoxide Sulfur-Resistant Shift Catalyst". It is the method standard for determining the activity, strength and wear rate of the catalyst product.
This standard is formulated based on relevant domestic and foreign data and the enterprise standards of relevant domestic catalyst manufacturers, on the basis of large-plate laboratory tests, and combined with the actual situation in my country. The appendixes A, B, C, D and E of this standard are all suggestive appendices. This standard is proposed by the Technical Supervision Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the fertilizer catalyst standardization technical centralized unit of the Ministry of Chemical Industry. The responsible drafting unit of this standard: Nanjing Chemical Industry (Group) Corporation Research Institute. Participating drafting units: Shanghai Chemical Industry Research Institute of the Ministry of Chemical Industry and Hubei Institute of Chemistry.
The main drafters of this standard are Kui Shibin, Zhang Lingxia, Shen Xingnan, Chen Jinsong and Gu Renxing. This standard was first issued on January 23, 1996. Foreword
2 Reference standards
3 Comprehensive determination
4 Determination of the crushing resistance of jade at one point
5 Determination of abrasion rate
6 Determination of cobalt and molybdenum content
Appendix A (suggestive appendix)
Appendix B (suggestive appendix)
Appendix C (suggestive appendix)
Appendix D (Suggestive Appendix)
Appendix E (Suggestive Appendix)
Determination of isothermal zone of converter
Correction of gas flow
Gas analysis and temperature control
Determination of bulk density of catalyst sample
Determination of volume ratio of water vapor to feed gas
1 Scope
Chemical Industry Standard of the People's Republic of China
Test method for sulfur-tolerant carbon monoxide shift catalyst HG/T 2780 - 1996
This standard specifies the activity, point pressure crushing resistance and attrition rate of sulfur-tolerant carbon monoxide shift catalyst products. Determination of cobalt content and calibration of activity test equipment.
2 Cited standards
The clauses contained in the following standards constitute the clauses of this standard by being cited in this standard. When this standard is published, the versions shown are valid. All standards will be revised. Parties using this standard should explore the possibility of using the latest versions of the following standards. GB/T3636--83 (88) Determination of attrition rate of fertilizer chemicals, molecular sieves and adsorbents HG/T2781-1996 Determination of cobalt and molybdenum content in sulfur-resistant shift catalysts HG/T2782-1996 Determination of crushing resistance of fertilizer catalyst particles Test method for medium-temperature shift catalysts for carbon monoxide ZB/T G74 001-89
3 Activity determination
3.1 Summary of the method
Carbon monoxide reacts with water vapor to generate carbon dioxide and hydrogen under the action of a catalyst. By measuring the change of carbon monoxide content in the inlet and outlet gases, the carbon monoxide conversion rate can be calculated. The chemical reaction formula is as follows: CO+H,O = CO++H2
3.2 Test conditions
Converter: This standard adopts a straight-through single-tube converter with an inner diameter of 32mm. The temperature measuring thermocouple sleeve should be at the catalyst bed inlet interface (see Figure 1 converter schematic diagram): Gas inlet
2: 0000000
1-Thermocouple sleeve width: 2-Catalyst bed: 3-Glass ball filler Figure 1 Converter sampling diagram
Catalyst particle size: original particle sample with a diameter of 4.0mm~5.0mm; Catalyst device: 30mL;
Operating pressure: 0.8±0.02MPa:
Space velocity: 2500±50h-1;
Activity test temperature: 200± 1C;
1996-01-23 Ministry of Chemical Industry of the People's Republic of China approved gas export
1997-01-0t implementation
HG /T 2780—1996
Volume ratio of water vapor to raw gas: 0.5±0.02; Raw gas composition (V/V): carbon monoxide 28%~32%, carbon dioxide 6%~10%, hydrogen 38%~42%, oxygen less than 0.5%, total sulfur (in terms of H, S) greater than 0.1g/Nm, and the rest are inert gases 3.3 Test device flow
The activity test device flow is shown in Figure 2.
1-steel cylinder; 2-activated carbon purifier: 3-1, 3-2, 3-3 flow meter: 4-CS, evaporator; 5-gas combination bottle
6-glass bottom bottle: 7-water metering tube: 8-flow pump: 9-vaporizer: 10-insulation tube: 11-converter 12-condensation separator; 13-desulfurizer purifier: 14-1, 14-2 water seal bottle: 15-alkali washing bottle: 16-chromatogram only Figure 2 Schematic diagram of the process of carbon monoxide sulfur-resistant conversion agent activity test device 3.4 Active 34.1 Sample preparation and converter filling
According to the provisions of Appendix D (suggested Appendix), obtain the bulk density, then weigh a sample equivalent to 30mL for use, put the processed glass ball filler with a diameter of 3-5mm into the converter, tap and vibrate gently, fill to the specified height, add a layer of alloy sieve plate, pour the prepared sample, tap the tube wall gently to make the catalyst bed surface flat, and ensure that the bed height is 39±1mm, and it is located in the isothermal zone of the converter. Add another layer of alloy sieve plate, and finally add a little filler, tighten the converter nut 3.4.2 Test system leak test
Connect the converter to the test system, open the raw gas main, feed the raw gas into the system, stabilize the pressure at 0.8MPa, close the system inlet and outlet valves, make the system in a sealed state for leak test, and the test can be carried out only after the leak test is qualified. After the leak test is completed, open the system outlet valve to exhaust the air, and the system drops to normal pressure.
3.4.3 Preparation of temperature measurement and temperature control system
Insert the temperature measurement thermocouple into the thermocouple sleeve in the converter, and make the hot end of the humidity measurement thermocouple be located 5mm away from the catalyst bed at the gas inlet.
Check the instruments and meters of the temperature measurement and temperature control system to ensure that they are in normal operation. 3.4.4 Catalyst sulfidation
The active component of the cobalt-molybdenum series carbon monoxide sulfur-resistant shift catalyst is in an oxidized state before testing, and is inactive or has very low activity. It needs to be converted into a sulfided state through sulfidation to show normal activity. The sulfurization reaction formula is as follows:
HG/ T 2780 —1996
Mo0,+cS,+5H,=Mos,+CH,+3H,o
9Co0+4CS2+17H,-Co,S,+4CH++9H,0Sulfurization steps:
Pass raw gas into the converter. The air velocity is 750h-, the system pressure is normal pressure, and the temperature rise sulfurization operation index is according to Table 1. When the converter temperature rises to 180, start to add CS or H,S with a total sulfur (in terms of HS) of 50-70/Nm into the raw gas, and stop adding sulfur when the converter temperature drops from 420C to 250c, and the sulfurization is completed. Table 1 Sulfurization operation index
Converter temperature range,
Room temperature~250
250-330
350~420
420~250
3.4.5 Activity test
Heating rate,/h
Time required for natural drop
h
After the vulcanization is completed, the vaporizer and the insulation pipe are powered on for heating. The vaporizer is controlled at 280±20℃ and the insulation pipe is controlled at 180±10℃. The raw gas main is opened, and the system is ventilated through the pressure regulating valve. The flowmeter at the outlet of the converter is adjusted to control the float of the flowmeter on the specified scale. The system pressure is slowly adjusted to increase the system pressure within half an hour and stabilize it at 0.8±0.02MPa. While passing the raw gas, the horizontal flow pump is started to inject water into the vaporizer to control the steam-gas ratio to 0.3±0.02. The converter overflow is further reduced to 200±1℃ and the temperature is kept constant.||t t||Control and adjust the above system pressure, air velocity, steam-gas ratio, temperature and other test conditions. After stabilization for 4 hours, analyze the carbon monoxide content in the converter inlet and outlet gas every 1.5-2.0 hours and calculate its conversion rate. Analyze three times in a row. If the absolute difference in conversion rate is no more than 1.0% and there is no obvious upward or downward trend, the analysis is considered stable and the test can be ended. First, close the main valve of the raw gas, empty the system to reduce pressure, and discharge the condensed water in the condenser at the same time. When the system drops to normal pressure, cut off the horizontal flow pump, stop water injection, and finally cut off all power supplies in the system. 3.4.6. Expression of test results
The carbon monoxide sulfur-tolerant shift catalyst activity expressed as the carbon monoxide conversion rate E is calculated according to formula (1): E
Vco ×(1+ 'co)
Wherein: Vco——the volume percentage concentration of carbon monoxide in the feed gas; y'co
the volume percentage concentration of carbon monoxide in the shift gas; Determination of 4-point crushing resistance
4.1 Measuring instrument
Range: 0～250 N;
x 100%
Accuracy: Class 1;
Force application speed: 5N/S.
HG/T2780-1996
4. 2 Number of particles to be measured
No less than 40 particles of catalyst sample with a diameter of 4.0-5.0mm are taken for measurement (sieved with a test sieve with a pore size of 4.00mm and 5.00mm in accordance with GB/T6003 "Test Sieve"). 4.3 Determination
The point pressure crushing resistance is measured according to the method specified in HG/T2782. 5 Determination of abrasion rate
Abrasion rate is measured according to the method specified in GB/T3636, where the sample with a diameter of 4.0 is taken. ~5.0.mm catalyst sample (sieved with test sieves with apertures of 4.00mm and 5.00mm in accordance with GB/T6003 "Test Sieve") 6: Determination of cobalt and silver content
The content of cobalt oxide and aluminum trioxide in the catalyst shall be carried out in accordance with HG/T2781, 12
Appendix A (Suggested Appendix)
Determination of the isothermal zone of the converter
A1 In order to test the activity of the catalyst, the catalyst must be installed in the isothermal zone of the converter. For the converter that is newly made or replaced with the heating electric furnace wire or when an abnormality is found during the inspection, the isothermal zone must be measured. The isothermal zone measurement shall be carried out at least once a year. A2 Fill the converter with glass balls with a diameter of 3 to 5mm, tighten the nuts, connect it to the activity test system, test the pressure and leak until it is qualified, and insert the thermocouple into the thermocouple sleeve. A3 Heat the converter to a constant temperature of 200±5℃ at a heating rate of about 50℃/h. At the same time, ventilate and pressurize the test system, power on and heat the vaporizer and insulation pipe, start the horizontal flow pump to inject water into the vaporizer, so that the temperature, pressure, airspeed and steam-gas ratio of the test system all meet the requirements of the test conditions of this standard. After the above conditions are stable for 2 hours, start to measure the isothermal zone. A4 records the length of the thermocouple inserted into the thermocouple sleeve and the corresponding overflow, that is, the temperature at the origin. First, insert the thermocouple into the thermocouple tube. Wait for about one minute for each 10mm inserted, and record the temperature after stabilization. Continue to insert it until the temperature difference is more than 2C after the thermocouple is inserted to a certain point. Then pull the thermocouple outward. Wait for about one minute for each 10mm pulled out, and record the temperature after stabilization. Pull them out in sequence until the temperature difference is more than 2C after the thermocouple is pulled to a certain point. Then insert the thermocouple into the thermocouple sleeve again, using the above method, until the thermocouple is inserted to the origin for one measurement, A5. Repeat the measurement once according to the method of A4, and take the common isothermal zone of the two measurements, which is the isothermal zone of the converter. A6 Sometimes the measured overflow does not show the isothermal zone. The heating furnace of the converter needs to be removed, the density position of the electric furnace wire is adjusted, and then the isothermal zone is re-measured to make the temperature difference in the isothermal zone not greater than 1°C and the length of the isothermal zone not less than 60mm. A7 According to the length of the isothermal zone, determine the height of the glass balls at the bottom of the converter and the catalyst loading position. The top end of the temperature measuring thermocouple sleeve is located at the interface between the catalyst bead layer and the gas inlet, and the insertion length of the thermocouple is calculated. 13
Appendix B (Suggested Appendix)
Gas flow correction
The size of the gas flow disk directly affects the activity of the catalyst. Therefore, when a new flow meter is used or the room temperature changes greatly or the activity shows abnormal phenomena, the flow of the rotor flow meter needs to be corrected. The air velocity in the test conditions of this standard is measured with the raw gas. Since the test is carried out under pressurized conditions, the atmospheric flow meter cannot be used. It can only be measured with the tail gas after decompression, that is, the conversion gas. Therefore, it is necessary to convert the gas volume of the conversion gas equivalent to the raw gas according to the carbon monoxide conversion rate for correction. The correction method uses the wet gas flow meter measurement method. B1 Conversion of conversion gas and raw gas flow
Convert according to (BI):
q. =-g,(1 + V
武中：4a—conversion gas flow rate, L/min; q——raw gas flow rate, L/min;
Vco—carbon monoxide volume percentage concentration in raw gas; carbon monoxide conversion rate,
B2The calculation and correction method of gas flow correction shall be carried out according to the method specified in Appendix C of ZB/TG7400114
Appendix ℃ (suggested appendix))
According to Appendix E of ZB/TG74001.
Gas analysis and temperature control
Appendix D (Appendix of Suggestions)
D1: Sample processing
Determination of bulk density of catalyst sample
Use test sieves with apertures of 4.00mm and 5.00mm in accordance with GB6003 "Test sieve" to sieve the sample, and take the sample with d4.0mm~d5.0mm for testing
D2 Accumulation of samples
Divide the sample to be tested into five portions, each of which is about 20mL, and add them into a 250mL measuring cylinder in turn. Each time you add, vibrate the measuring cylinder up and down several times. , until the position of the sample in the measuring cylinder remains unchanged, and the final compacted sample disk is 100mL. Weigh the mass of the 100mL sample after compaction (accurate to 0.1g).
D3 Calculation of bulk density
Bulk density is calculated according to formula (D1):
where: e
bulking density, milliliter/mL;
the mass of the measuring cylinder plus the mass of 100mL sample, g:m, the mass of the measuring cylinder, gi
V-—volume of the sample, mL.
D 4 Take the arithmetic mean of the parallel determination results as the determination result. The absolute difference of the parallel determination results shall not exceed 0.02 g/mL. 16
Appendix E (suggested appendix)
Determination of the volume ratio of water vapor to raw gas The volume ratio of water vapor to raw gas has a great influence on the carbon monoxide conversion rate. Therefore, it is very necessary to maintain the ratio within a certain range. The activity test device of this standard uses a horizontal flow pump to quantitatively pump water into the vaporizer. The water is completely vaporized in the vaporizer and mixed with the raw gas to form a mixed gas of a certain ratio that enters the converter for conversion reaction. E1 Determination process
The determination process is shown in Figure 2 of this standard.
E2 Determination process
E 2. 1 Determination of water consumption rate
Start the horizontal flow pump and set the flow rate of the horizontal flow pump to a certain value. After the system is stable for 10mi, close the outlet cock of the glass bottom bottle. Only allow the water in the measuring tube to enter the horizontal flow pump, record the initial reading of the water in the measuring tube () and start timing with a stopwatch at the same time. When the time reaches about 10 minutes, record the final reading of the water in the metering coil (h). Calculate the water consumption rate (4*) according to formula (E1):
h,—h,bzxz.net
Where: 4water—water consumption rate, mL/min;—final reading of water, mL;
h, initial reading of water, mL;
Time used for determination, min.
E2.2 Determination of the flow rate of raw gas after condensation and separation (E1)
While starting the horizontal flow pump, feed the raw gas into the system (the converter is fully filled with packing), control the flow of the raw gas at a certain position, pass cooling water into the condenser, keep the system stable, and measure the water While measuring the consumption rate, record the starting reading of the wet gas flow meter (V,) and use a stopwatch to record the time at the same time. When the time reaches about 10min, record the ending reading of the wet gas flow meter (V,). Calculate the raw gas flow rate according to formula (E2) (4):
Where: 9—the flow rate of raw gas under the measurement conditions, L/min; V2——the ending reading of the wet gas flow meter, L; V——the starting reading of the wet gas flow meter, L; the time used for measurement, min.
E2.3 Calculation of the volume ratio of water vapor to raw gas Follow formula (E3) to calculate:
P ×4*×1. 244
Wherein: R—volume ratio of water vapor to raw gas: density of water at room temperature T, g/mL;
—water consumption rate, mL/min;
—the corresponding volume of water vapor produced by 1g water under standard conditions, L/8—the flow rate of raw gas under the measurement conditions, .L/min;—the conversion coefficient of the raw gas volume under the measurement conditions to the volume under standard conditions, calculated according to formula [E4) f
Wherein:
p+p,- P2
is the atmospheric pressure at the time of measurement, MPa;
is the pressure of the mercury manometer on the wet gas flowmeter, MPa; P is the saturated water vapor partial pressure when the temperature is T, MPa; P
is the atmospheric pressure under standard conditions, MPa
is the temperature under standard conditions, K;
is the temperature at the time of measurement, K.
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