Some standard content:
Standard of the Ministry of Chemical Industry of the People's Republic of China, Type B202 Low-Temperature Shift Catalyst
HG1-1315-80
Group 11
Transfer 3556—1930
This standard applies to Type B202 low-temperature shift catalyst for producing hydrogen by adding carbon monoxide to water vapor in synthetic ammonia and hydrogen production equipment. External
diameter, mm
Physical properties
Chemical composition
(original base)
Quality indicators
Length, m
Bulk density, kg/L
Specific surface area, m/g
Copper oxide (CuO) content, %
Zinc oxide (ZnO) content, %
Aluminum oxide (AI,O,) content, %
The activity and mechanical strength of this product must meet the following requirements: Initial activity: outlet CO
Activity after heat resistance: outlet CO
Mechanical strength: average lateral compression strength
2 Acceptance specifications
Black glossy cylinder
60~80 (before use)
≥16 kgf/cm.
2.1 The products in this standard shall be inspected by the technical inspection department of the manufacturer. The manufacturer shall ensure that all the products leaving the factory meet the requirements of this standard. Each batch of products leaving the factory shall be accompanied by a product certificate in a certain format. 2.2 Inspections shall be conducted no less than twice a month, and the representative quantity each time shall not exceed 10 tons. 2.3 Sampling method: The inspection department shall be responsible for taking out a representative sample of about 3 liters from 20% of each batch of products and placing it in a stoppered glass bottle. The representative sample taken out shall be fully mixed and averaged by the quartering method, and divided into chemical analysis, activity, strength evaluation and preservation samples. Labels shall be attached to the sample bottles, indicating the product name, model, batch number, representative quantity, sampling date, and sampler. The preservation samples shall be kept for years for assessment. 2.4 If the product fails the inspection, the inspection device, temperature control instrument, flow and analytical instrument, etc. shall be calibrated and re-inspected. If it is still unqualified, it is allowed to re-sample and inspect the batch of products according to the provisions of 2.3. The re-inspection results show that even if only one indicator does not meet the requirements of this standard, it cannot be shipped as a qualified product. 2.5 If the user has any objection to the quality of the received catalyst, it has the right to inspect it according to the quality indicators in Chapter 1 and the inspection rules and methods specified in 2.3, 3.1, and 3.2 to verify whether its indicators meet the requirements of this standard, or request arbitration from relevant units. 3 Test method
3.1 Activity determination
3.1.1 Principle: Carbon monoxide and a certain proportion of water vapor generate hydrogen and carbon dioxide under the catalytic action of low-flow shift catalyst. The chemical reaction formula is:
CO+H,OCO+H2+9.8 kcal/g molecule (25℃) 3.1.2 Activity test process: as shown in Figure 1 Ministry of Chemical Industry of the People's Republic of China
July 1, 1980
Research Institute of Nanhua Company
HG1-1315-80
Figure 1 CO low-temperature shift catalyst activity test flow rate 25
1—Raw gas cylinder; 2-Pressure relief valve: 3-1—Cylinder outlet valve: 3-2—Gas block valve; 3-3.3-4—Wet gas valve: 3-5, 3-6—Dry gas valve: 3-7—Vent cabinet: 4-1-Silica gel dryer: 4-2—Active Carbon desulfurizer: 4-3—molecular sieve purifier 5—bellows pressure regulating valve; 6-1~6-5 electromagnetic room: 7—desulfurization furnace, 8-1~8-4—rotor flowmeter: 9-1.9-2—saturator; 10—water bath: 11—precision thermometer, 12—adjustable electric contact thermometer, 13—electronic maintenance appliance 14-1.14-2—reactor, 15—heating furnace: 16—temperature recorder: 17-1—temperature measuring thermocouple ：17-2-Control thermocouple: 18-1, 18-2-Condenser; 19-1.19-2-Gas-water separator; 20-Downstream water tank, 21-Glass cock + 22-Standard gas zero point gas, inlet for infrared analyzer calibration; 23-Silica gel drying tube; 24-Infrared CO analyzer; 25-Evacuation P, P, pressure gauge 3.1.3 Inspection conditions:
Catalyst device: 3 ml (particle size 20-40 mesh). Pressure: Normal pressure.
Space velocity: 4000 h-1
Temperature: 200℃.
H, O (steam)/CO.6.
Raw gas composition: CO~5%, CO2~2%, the rest is pure gas (dry gas) with a ratio of hydrogen and nitrogen of three. Heat-resistant temperature and time: 400℃ for 2 hours. 3.1.4 Inspection process
Crush the sample and pass it through a 20-40 mesh sieve. Use a 10-liter measuring cylinder to pile up 3 ml tightly, then weigh it to obtain the bulk density. Load the furnace, and pile up the pre-treated clean quartz sand (16-18 days) tightly to the specified size, and then pour the weighed 3 ml catalyst into the reactor (see Figure 2). Use a wooden hammer to gently knock the reactor to make its surface flat, then add quartz sand to the mouth of the reaction tube, tighten the nut, and connect the reactor to the system.
c. Insert the thermocouple into the isothermal layer, which is equivalent to 5 mm below the catalyst layer. d. Temperature reduction
The B202 catalyst composed of copper, zinc, and aluminum oxides must be reduced to metallic copper by H. or CO to be active. The reduction heat of copper oxide is equivalent to 21 kcal/g molecule copper. Since a large amount of heat will be released, and copper catalysts are sensitive to heat, the reduction temperature must be strictly controlled in order to obtain good catalytic activity. 301
HG1-1315-80
Figure 2 Schematic diagram of reactor structure
1-Gas outlet pipe; 2-Simplified; 3-Square; 4-Core: 5-Handling cap; 6-Gas inlet pipe Low-temperature catalyst is also very sensitive to poisons such as sulfur and chlorine. If the raw gas contains sulfur, the desulfurization furnace must be heated first to desulfurize the raw gas through the desulfurization furnace, and the sulfur content is less than 1PPM before entering the low-temperature reactor. Heating reduction conditions: normal pressure, raw gas 500h-1 (thousand gas). Heating rate: room temperature to 120℃, 1.5 hours; 120℃ to 200℃ 4 hours.
Activity measurement can be carried out after switching to wet gas (with water vapor) and stabilizing for 2 hours. e. Activity determination: During the catalyst reduction period, the water bath can be heated to the required water vapor temperature. After the reduction is completed, switch to wet gas. Under the conditions of furnace temperature of 200℃, steam/C0=6, and air velocity of 4000 h-, the initial activity determination is carried out after stabilization for 2 hours. Generally, the outlet CO is analyzed once every half an hour, and 5 to 6 or more data are analyzed. If the difference in the outlet CO for 3 consecutive analyses is not greater than 0.02%, the analysis can be considered stable. After the initial activity determination is completed, the furnace temperature is quickly (about 1 hour) raised to 400℃ for 2 hours of heat resistance, and then lowered back to 200℃. After stabilization for 2 hours, the activity determination after heat resistance can be carried out. The outlet CO is analyzed according to the above regulations, and the furnace is stopped after the analysis is completed. f. Before stopping the furnace, cut off all power supplies of the system, then close the main gas valve, and unplug the converter outlet hose. 3.2 Mechanical strength determination
Use Q2-20 catalyst pressure tester, adopt the "random casting" sampling method, take out no less than 20 samples from the representative sample, and measure the length (cm) of each sample with a micrometer. Use a pressure measuring instrument to measure the side crushing load (kg) of each catalyst. The quotient obtained by dividing the crushing load of each particle by the length of each particle is the side pressure strength (kgf/cm) of each catalyst. The average is the average side pressure strength (kgf/cm). 4 Packaging, marking, storage, and transportation
4.1 B202 low-transformation catalyst should be packed in an iron barrel lined with a plastic bag. It must be sieved before packaging to remove powder and fragments in the finished product. The net weight of each barrel of catalyst is 50 kg
4.2 The packaging barrel should be painted blue and firmly marked with yellow paint. The content: product name, model, net weight (kg), gross weight (kg), batch number, manufacturer name, and indicate the words "handle with care and prevent moisture". 4.3 The packaged products should be sealed and stored in a dry warehouse to prevent moisture and contamination. Rolling and shaking are strictly prohibited during transportation. 302
HG1-1315-80
Appendix A
Reactor temperature control and determination of isothermal layer (reference)
A1 Reactor temperature control: The reactor temperature control can be carried out by using nickel-chromium-nickel-aluminum thermocouples in conjunction with the DWT702 temperature controller of Shanghai Instrument Factory No. 6 or other temperature automatic controllers. The water bath uses a conductive meter and a relay to control the saturator temperature. A2 Determination of reactor isothermal layer
The reaction tube inner diameter of the low-temperature catalyst type B202 is a tubular reactor with a diameter of 10 mm. For a new reactor, its isothermal zone must be measured first to determine the position of the catalyst. The measurement steps are as follows: A2.1 Fill the reaction tube with 16-18 mesh clean quartz sand, tighten the screw sheath and connect it to the system. A2.2 After connecting according to the detection process, start heating the reactor and water bath, and pass low-temperature raw gas with an air velocity of 4000 h-. A2.3 When the reactor temperature reaches 200℃ and the saturator temperature is about 60C, start measuring the isothermal zone after stabilizing for 2 hours, and record the temperature and the length of the thermocouple inserted into the converter. A2.4 Pull the thermocouple outward first, and pull out a section of porcelain tube (about 10 mm) each time. After one minute, wait for the temperature to stabilize and record the temperature and the number of sections of porcelain tube. Pull until the temperature changes significantly, then return the thermocouple and insert it inward. Similarly, record the temperature once for each section of porcelain tube inserted until the temperature changes significantly. To confirm the measured results, measure again according to the above procedures. According to the temperature distribution obtained by pulling out and inserting the thermocouple, determine the point with close temperature as the isothermal zone. If the measured data does not show an isothermal zone, the reactor needs to be disassembled and the density of the electric furnace wire needs to be readjusted, and then measured again. The isothermal zone of the reactor is required to be longer, and for the reactor of the 3 ml device, it is required to be more than 45 mm. Appendix B
Determination of the ratio of water vapor to raw gas and calculation of saturated water vapor temperature (reference)
B1 Determination of the ratio of water vapor to raw gasbZxz.net
B1.1 Determination principle: The principle that the steam in the mixed gas of conversion gas and steam can be condensed into water and separated from the conversion gas is used. The mixed gas is first cooled by a condenser to condense the steam into water and gather in a graduated glass tube, while the conversion gas is measured by a wet flow meter and then discharged. This method can directly and continuously determine the steam ratio in the tail gas after the reactor during the activity test. B1.2 Determination procedure: According to the process shown in Figure B1, first let cold water pass through the condenser, then let the tail gas after the reactor pass through the condenser, record the starting number on the flow meter, the gas temperature and pressure on the flow meter, and record the atmospheric pressure at that time, and stop ventilation when the condensed water collected in the graduated measuring tube reaches a certain volume. Record the second reading on the flow meter, and the volume of the gas can be obtained from the difference between the two readings on the flow meter. 303
HG1-1315—80
Figure B1 Water vapor and raw gas ratio measurement device 1-conversion gas inlet; 2-cooler: 3-cooling water collector: 4-mercury pressure gauge; 5-thermometer; 6-temperature flow meter B1.3 Calculation:
Steam/conversion gas, n=W+×2/V
When the flow meter temperature is high, the water vapor carried away by the gas must be corrected. 22.4
Steam/conversion gas=（W*+WV）×
W*-weight corresponding to the collected condensed water volume (grams); W-grams of water carried away by each liter of gas at room temperature; Vstandard-the volume of ventilation under standard conditions:
-ventilation volume (liters).
The ratio of steam to raw gas is calculated by the following formula: 273
(liters)
steam/raw gas=n+（n+1)α
Wherein: n--the ratio of steam to conversion gas reflects the percentage concentration of carbon monoxide.
B.2 Calculation of saturator temperature control
According to the detection requirements, steam/CO=6, and the raw gas contains 4% CO, then steam/gas=6×4%=0.24
Assume that the atmospheric pressure is 760 mmHg, then the water vapor pressure at this time is: 0.24
-147 (mmHg)
According to the water vapor pressure table, the corresponding temperature of 147 mmHg water vapor pressure is ~60℃, which is the temperature at which the saturator controls the humidity when steam/CO=6 and CO4%.
When the steam/CO or CO concentration in the raw gas changes, the water vapor partial pressure under this condition must be recalculated, and the corresponding saturator temperature can be obtained by looking up the table.
C1 Calibration method
HG1-1315-80
Appendix C
Calibration of orifice flowmeter
(reference)
Let the gas pass through the orifice flowmeter and then enter the wet flowmeter. Use orifices of different sizes to adjust the pressure difference to the required gas volume, and then measure the required air velocity.
C2 Calibration device See Figure C1
Figure C1 Calibration device of orifice flowmeter
1—Gas cock 2—Gas volume adjustment cock: 3—Orifice flowmeter: 4—Mercury thermometer; 5—Thermometer: 6—Wet flowmeter C3 Calibration steps
C3.1 Adjust the wet flowmeter to a horizontal state, check the water level of the flowmeter, and open the overflow cock. C3.2 Convert the gas flow rate under standard conditions to the flow rate under the current conditions. The conversion formula is as follows: V. -SVxVat
by oePy
where: V. Gas flow rate under standard conditions (ml): V
Gas flow rate under the current conditions (ml); Operating space velocity (hour-1);
Catalyst loading volume (ml);
Standard atmospheric pressure (mmHg):
Water vapor pressure at atmospheric pressure minus t℃ + P city; Temperature under standard conditions (273K);
Temperature under the current conditions (T=273+t℃); Flow meter pressure.
C3.3Open the raw gas cock 1, use cock 2 to adjust the gas volume passing through the wet flow meter, and record the starting reading on the wet gas flow meter. At the same time, press the stopwatch and stop it immediately when the calculated gas volume passes. Check whether the measured time is just right. If it is just right, recheck it once, and then mark the pressure difference height of the sharp orifice flow meter. This pressure difference represents the flow rate under the current conditions. Normal inspection is based on this pressure difference height. If the time and flow rate are not just right, the pressure difference of the orifice flowmeter needs to be adjusted or the orifice glass needs to be replaced until the flow rate and time match.
When the room temperature changes greatly or abnormal phenomena occur in the activity test, the gas flow rate needs to be corrected. Appendix D
Gas Analysis Method
(Reference)
In the process of low-speed catalyst activity test, CO in the raw gas and CO at the reactor outlet must be analyzed. The analysis method can be QGS carbon monoxide infrared analyzer or gas chromatograph. The full analysis of the raw gas uses a gas chromatograph or Ostwald gas analyzer. The zero point and sensitivity of the infrared analyzer must be calibrated frequently when in use. The gas chromatograph can use 13X, 5A or carbon molecular sieve as the separation column, and the concentration of the standard gas used must be accurate. The absorption liquid used for Ostwald analysis must be replaced regularly. For the analysis of trace total sulfur in the raw gas, organic sulfur compounds can be hydrogenated into hydrogen sulfide under high temperature platinum catalysis, and then absorbed by potassium hydroxide solution. The sulfur ions in the absorption liquid are measured by mercury titration with disulfide as an indicator, and the total sulfur content is calculated.4
Steam/converted gas=（W*+WV）×
W*-weight (g) corresponding to the volume of condensed water collected; W-grams of water carried away per liter of gas at room temperature; Vstandard-volume of ventilation under standard conditions:
-ventilation volume (liter).
The ratio of steam to raw gas is calculated by the following formula: 273
(liter)
Steam/raw gas=n+（n+1)α
Where: n-the ratio of water vapor to converted gas reflects the percentage concentration of carbon monoxide.
B.2 Calculation of saturator temperature control
According to the detection requirements, steam/CO=6, and the raw gas contains 4% CO, then steam/gas=6×4%=0.24
Assume that the atmospheric pressure is 760 mmHg, then the water vapor pressure at this time is: 0.24
-147 (mmHg)
According to the water vapor pressure table, the corresponding temperature of 147 mmHg water vapor pressure is ~60℃, which is the saturator humidity control when steam/CO=6 and CO4%.
When the steam/CO or CO concentration in the raw gas changes, the water vapor partial pressure under this condition must be recalculated, and the corresponding saturator temperature can be obtained by looking up the table.
C1 Calibration method
HG1-1315-80
Appendix C
Calibration of orifice flowmeter
(reference)
Let the gas pass through the orifice flowmeter and then enter the wet flowmeter. Use orifices of different sizes to adjust the pressure difference to the required gas volume, and then measure the required air velocity.
C2 Calibration device See Figure C1
Figure C1 Calibration device of orifice flowmeter
1—Gas cock 2—Gas volume adjustment cock: 3—Orifice flowmeter: 4—Mercury thermometer; 5—Thermometer: 6—Wet flowmeter C3 Calibration steps
C3.1 Adjust the wet flowmeter to a horizontal state, check the water level of the flowmeter, and open the overflow cock. C3.2 Convert the gas flow rate under standard conditions to the flow rate under the current conditions. The conversion formula is as follows: V. -SVxVat
by oePy
where: V. Gas flow rate under standard conditions (ml): V
Gas flow rate under the current conditions (ml); Operating space velocity (hour-1);
Catalyst loading volume (ml);
Standard atmospheric pressure (mmHg):
Water vapor pressure at atmospheric pressure minus t℃ + P city; Temperature under standard conditions (273K);
Temperature under the current conditions (T=273+t℃); Flow meter pressure.
C3.3Open the raw gas cock 1, use cock 2 to adjust the gas volume passing through the wet flow meter, and record the starting reading on the wet gas flow meter. At the same time, press the stopwatch and stop it immediately when the calculated gas volume passes. Check whether the measured time is just right. If it is just right, recheck it once, and then mark the pressure difference height of the sharp orifice flow meter. This pressure difference represents the flow rate under the current conditions. Normal inspection is based on this pressure difference height. If the time and flow rate are not just right, the pressure difference of the orifice flowmeter needs to be adjusted or the orifice glass needs to be replaced until the flow rate and time are consistent.
When the room temperature changes greatly or abnormal phenomena occur in the activity test, the gas flow rate needs to be corrected. Appendix D
Gas Analysis Method
(Reference)
In the process of low-speed catalyst activity test, CO in the raw gas and CO at the reactor outlet must be analyzed. The analysis method can be QGS carbon monoxide infrared analyzer or gas chromatograph. The full analysis of the raw gas uses a gas chromatograph or Ostwald gas analyzer. The zero point and sensitivity of the infrared analyzer must be calibrated frequently when in use. The gas chromatograph can use 13X, 5A or carbon molecular sieve as the separation column, and the concentration of the standard gas used must be accurate. The absorption liquid used for Ostwald analysis must be replaced regularly. For the analysis of trace total sulfur in the raw gas, organic sulfur compounds can be hydrogenated into hydrogen sulfide under high temperature platinum catalysis, and then absorbed by potassium hydroxide solution. The sulfur ions in the absorption liquid are measured by mercury titration with disulfide as an indicator, and the total sulfur content is calculated.4
Steam/converted gas=（W*+WV）×
W*-weight (g) corresponding to the volume of condensed water collected; W-grams of water carried away per liter of gas at room temperature; Vstandard-volume of ventilation under standard conditions:
-ventilation volume (liter).
The ratio of steam to raw gas is calculated by the following formula: 273
(liter)
Steam/raw gas=n+（n+1)α
Where: n-the ratio of water vapor to converted gas reflects the percentage concentration of carbon monoxide.
B.2 Calculation of saturator temperature control
According to the detection requirements, steam/CO=6, and the raw gas contains 4% CO, then steam/gas=6×4%=0.24
Assume that the atmospheric pressure is 760 mmHg, then the water vapor pressure at this time is: 0.24
-147 (mmHg)
According to the water vapor pressure table, the corresponding temperature of 147 mmHg water vapor pressure is ~60℃, which is the saturator humidity control when steam/CO=6 and CO4%.
When the steam/CO or CO concentration in the raw gas changes, the water vapor partial pressure under this condition must be recalculated, and the corresponding saturator temperature can be obtained by looking up the table.
C1 Calibration method
HG1-1315-80
Appendix C
Calibration of orifice flowmeter
(reference)
Let the gas pass through the orifice flowmeter and then enter the wet flowmeter. Use orifices of different sizes to adjust the pressure difference to the required gas volume, and then measure the required air velocity.
C2 Calibration device See Figure C1
Figure C1 Calibration device of orifice flowmeter
1—Gas cock 2—Gas volume adjustment cock: 3—Orifice flowmeter: 4—Mercury thermometer; 5—Thermometer: 6—Wet flowmeter C3 Calibration steps
C3.1 Adjust the wet flowmeter to a horizontal state, check the water level of the flowmeter, and open the overflow cock. C3.2 Convert the gas flow rate under standard conditions to the flow rate under the current conditions. The conversion formula is as follows: V. -SVxVat
by oePy
where: V. Gas flow rate under standard conditions (ml): V
Gas flow rate under the current conditions (ml); Operating space velocity (hour-1);
Catalyst loading volume (ml);
Standard atmospheric pressure (mmHg):
Water vapor pressure at atmospheric pressure minus t℃ + P city; Temperature under standard conditions (273K);
Temperature under the current conditions (T=273+t℃); Flow meter pressure.
C3.3Open the raw gas cock 1, use cock 2 to adjust the gas volume passing through the wet flow meter, and record the starting reading on the wet gas flow meter. At the same time, press the stopwatch and stop it immediately when the calculated gas volume passes. Check whether the measured time is just right. If it is just right, recheck it once, and then mark the pressure difference height of the sharp orifice flow meter. This pressure difference represents the flow rate under the current conditions. Normal inspection is based on this pressure difference height. If the time and flow rate are not just right, the pressure difference of the orifice flowmeter needs to be adjusted or the orifice glass needs to be replaced until the flow rate and time match.
When the room temperature changes greatly or abnormal phenomena occur in the activity test, the gas flow rate needs to be corrected. Appendix D
Gas Analysis Method
(Reference)
In the process of low-speed catalyst activity test, CO in the raw gas and CO at the reactor outlet must be analyzed. The analysis method can be QGS carbon monoxide infrared analyzer or gas chromatograph. The full analysis of the raw gas uses a gas chromatograph or Ostwald gas analyzer. The zero point and sensitivity of the infrared analyzer must be calibrated frequently when in use. The gas chromatograph can use 13X, 5A or carbon molecular sieve as the separation column, and the concentration of the standard gas used must be accurate. The absorption liquid used for Ostwald analysis must be replaced regularly. For the analysis of trace total sulfur in the raw gas, organic sulfur compounds can be hydrogenated into hydrogen sulfide under high temperature platinum catalysis, and then absorbed by potassium hydroxide solution. The sulfur ions in the absorption liquid are measured by mercury titration with disulfide as an indicator, and the total sulfur content is calculated.
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