Some standard content:
Chemical Industry Standard of the People's Republic of China
Test methods for methanation catalysts
1 Subject content and applicable examples
HG/T2510-93
This standard specifies the test methods for the activity, particle crushing strength, attrition rate, ignition loss and wedge content of methanation catalysts. This standard is applicable to J101, J105 and J106Q methanation catalysts used in ammonia synthesis and hydrogen production series devices to oxygenate carbon oxides in the gas to produce methane.
2·Cited standards
GB/T3635 Determination method for crushing strength of fertilizer catalyst, molecular sieve and adsorbent particles GB/T3636 Determination method for attrition rate of fertilizer catalyst, molecular sieve and adsorbent GB6003 Test sieve
ZB/TG75003 Analysis method for loss on ignition of fertilizer catalyst HG/T2511 Analysis method for chemical composition of methanation catalyst HG/T2513 Test method for zinc oxide desulfurizer 3 Activity test
3.1 Principle of activity test
The hydrogen and nitrogen or high hydrogen gas of synthetic ammonia contains a small amount of carbon oxides, which generate methane under the action of methanation catalyst. The chemical reaction formula is as follows:
CO+3H2
CH+H,O
CO,+4H2-CH4+2H,0
3.2 Activity test process
The activity test process is shown in Figure 1. If there is no sulfur in the raw gas and the isothermal zone of the reactor can reach the required length, the desulfurization furnace and preheating furnace can be omitted.
Approved by the Ministry of Chemical Industry of the People's Republic of China on September 9, 19934
Implementation on July 1, 1994
HG/T2510-93
Figure 1 Schematic diagram of the activity test process
To analyze
To analyze
1-Hydrogen-nitrogen oil-water separator:: 2-Pressure regulating valve: 3-Desulfurization furnace: 4-Preheating furnace; 5-1, 5-2-Methanation reactor: 6-1, 6-2-Condenser;
3.3 Activity test conditions
7-1, 7-2—Flowmeter: 8—Gas distribution bottle (tank); This standard adopts a single-tube reactor. The activity test conditions are shown in Table 1. Table 1·Activity test conditions
Reaction tube specifications
Catalyst loading
Catalyst particle size
System pressure
Activity test temperature
Raw gas composition
Gas skin fraction
J 101. J 106 Q
Carbon dioxide cylinder
e38×3. 5mm
Original particle size
co,(1.2±0. 1)% The remainder is 3:1 Hydrogen nitrogen 7 000±200 hl
550±4c
4.5×10°h
Hydrogen and nitrogen
10000±200h-1
650±4c
8.0×10 h-1
3.4 Activity test process
3.4.1 Preparation of samples and filling of reactor HG/ T 2510 —93
Use a 1.70mm aperture test sieve (in accordance with the R40/3 series in GB6003) to sieve out the powder of the catalyst test sample, remove half of the sample, and then use a 250mL measuring tube to tightly stack 100mL of the complete particle virtual sample and weigh it to obtain the bulk density, and then weigh the sample equivalent to 30mL.
Put the treated 2-3mm quartz sand into the reaction tube, tap it gently to compact it, fill it to the specified height, add a layer of alloy mesh, pour the prepared sample and vibrate it, add another layer of alloy mesh, and finally fill it with quartz sand to the top of the thermocouple sleeve, and tighten the end screw of the reaction tube.
3.4.2 System leak test
Connect the filled reaction tube to the system, close all outlet valves and vent valves, pass hydrogen and nitrogen, raise the system pressure to 2.5MPa, stop ventilation, and see if the pressure does not drop within 5min. Otherwise, check with foaming liquid and treat the leak. After the test is qualified, the system pressure is released to normal pressure, and a thermocouple is inserted so that its end point is at the center point of the catalyst bed 10 mm away from the gas inlet.
3.4.3 Temperature reduction
The original conditions for catalyst temperature increase are shown in Table 2
Table 2 Temperature reduction conditions
Gas composition
J101.J106Q
4. 5×10° h-
400℃
3:1 Hydrogen and nitrogen
8. 0 × 10° h-
450℃
System hydrogen and nitrogen, cooling water is passed through the condenser, and the reduction conditions are controlled according to Table 2 to carry out temperature reduction of the catalyst; the preheating furnace and reactor are heated to the reduction temperature at any heating rate, and after the reduction is completed, the temperature is lowered to 300℃. The desulfurization furnace is heated to the desulfurizer use temperature at the same time; the newly used desulfurizer should be heated and reduced in advance. The reduction method refers to the HIG/T2513 zinc oxide desulfurizer test method. After the reduction is completed, it is lowered to the use temperature. The main chemical reaction equation of methanation catalyst reduction is as follows: Nio+H,
-Ni+H,O
3.4.4 Determination of pre-heat-resistant activity
Introduce the reaction raw gas, and raise the reaction pressure to 2.0MPa within 1 hour. Control the reaction temperature and air velocity according to Table 1. After each condition is stable for 2 hours, start analyzing the carbon dioxide content at the reactor outlet, and analyze it every 1 hour until the range of three consecutive analysis results is less than or equal to 10×10-6. Take the average of the three determination results after stabilization as the test result. 3.4.5 Heat resistance test
After the initial activity test, switch the raw gas to hydrogen and nitrogen, control the heat resistance test conditions according to Table 1, and heat up to the heat resistance temperature at any heating rate. After the heat resistance test, cool down to 300℃. 3.4.6 Determination of activity after heat resistance
The determination of activity after heat resistance is carried out in accordance with 3.4.4.6
Determination of crushing strength of particles
4.1 Measuring instrument
Range: 0～250 N
Accuracy: Class 1
Force speed: 5N/s
4.2 Strength determination
HG/T2510—93
The crushing strength of particles is measured and calculated according to the method specified in GB/T3635. The number of particles should be no less than 40. 5 Determination of wear rate
5.1 Determination method of wear rate
The wear rate shall be determined in accordance with the method specified in GB/T3636. 5.2 Determination conditions
Speed: 25±1 r/min
Number of revolutions: 500
Wear cylinder size (inner diameter×length): 50mm×300mmSample load: 40±2g (accurate to 0.01g) 6 Determination of loss on ignition
The loss on ignition shall be determined in accordance with the method specified in GB/T TG75003. 7 Determination of nickel content
The nickel content (Ni) shall be determined in accordance with the method specified in HG/T251I. HG / T 2510 — 93
Attached beam A
Determination of isothermal zone of reactor
(reference part)
, A1 In order to test the activity of the catalyst, the catalyst must be installed in the isothermal zone of the reactor. For the reactor newly made or replaced with electric furnace wire or when abnormalities are found during detection, the isothermal zone must be measured, and the isothermal zone measurement shall be conducted at least once a year. A2 Fill the reactor tube with 2 to 3 m of quartz sand, tighten the nut, connect it to the activity detection process, insert the thermocouple into the thermocouple guide tube, start heating,
A3 Hydrogen and nitrogen are passed through the reactor, and the air velocity is adjusted to 7000h-l (J101, 106Q), 10 000h-l (I105), and the pressure is 2.0MPa. Heat to the active test temperature, keep constant for 2 hours and then start the measurement. A4 inserts the thermocouple into the thermocouple tube, records its length and corresponding temperature, and uses this as the temperature at the origin. First pull the thermocouple outward, wait for about 2 minutes for each 10mm pullout, and record the stable temperature until the temperature difference is more than 2C. Then insert the thermocouple into the sleeve, wait for about 2 minutes for each 10mm insertion, and record the stable temperature until the thermocouple is inserted to the origin.
A5 Repeat the measurement once according to the method of A4, and take the common isothermal zone of the two measurements (temperature difference is less than or equal to 1C) as the isothermal zone at this temperature.
A6 Raise the reactor temperature to the heat-resistant temperature, the pressure is normal pressure, and after stabilization for 2 hours, measure the isothermal zone at the heat-resistant temperature according to the methods of A4 and A5, and take the common isothermal zone of the active test temperature and the heat-resistant temperature as the isothermal zone of the reactor. The length of the isothermal zone should be greater than or equal to 50 mm.
A7When the measured temperature does not show the isothermal zone, the heating part of the reactor needs to be removed, the density of the electric furnace wire needs to be adjusted, and then the isothermal zone needs to be remeasured.
A8Based on the measured length of the isothermal zone, determine the height of the quartz sand filled at the bottom of the reaction tube and the catalyst filling position, and calculate the insertion length of the thermocouple.
Appendix B
Determination of bulk density of catalyst
(reference)
B1 Divide the sieved complete particle sample into several portions and add them into a 250mL measuring cylinder in turn. Each time, vibrate the measuring cylinder up and down several times. Repeat the operation until the compacted sample volume is 100mL. B2 Weigh the sample and measuring cylinder with a balance to an accuracy of 0.1g. B3 Calculation of bulk density
The bulk density of the catalyst is calculated according to formula (B1).
m, -m
Where: p—bulk density, g/mL;
m——mass of the measuring cylinder, gi
mass of the measuring cylinder plus the mass of 100mL sample, g, V--volume of the sample, mL.
HG /T 2510 —93
B4 Take the average of two parallel measurement results with a relative deviation less than or equal to 0.2% as the measurement result. Appendix C
(reference)
The size of the gas flow disk directly affects the activity of the catalyst. When the room temperature changes greatly or the activity shows abnormal phenomena, the flow disk meter must be calibrated. The calibration method should preferably be the measurement method of the astringent gas flow meter. C1·Calculation of gas flow
C1.1 According to the catalyst loading and the specified space velocity, the volume of gas passing through every minute under standard conditions is calculated according to formula (C1): +.y+Yt
1000×60
Where: V.
The volume of gas passing through every minute under standard conditions, L; - space velocity, hl;
Catalyst loading, L,
C1.2 Convert the gas flow under standard conditions to the gas flow under the current conditions, and calculate V according to formula (C2): V-
P,Y.
The volume of gas passing through every minute during measurement, L: - atmospheric pressure under standard conditions, Pa; bzxZ.net
Actual atmospheric pressure at time, Pa;
- temperature under standard conditions, 273K;
- temperature during measurement, (T=T.+room temperature) K; V——the volume of gas passing through every minute under standard conditions, LC2 Wet gas flowmeter measurement method
C2.1 Connect the wet gas flowmeter and the flowmeter to be calibrated according to Figure C1 3
Figure C1 Wet flowmeter measurement method calibration loading (c)
2-gas volume regulating valve; 3-calibration flowmeter: 4-mercury pressure gauge; 5--overflow meter; 6-wet gas flowmeter 1-raw gas inlet valve; 2
HG /T 2510-93
C2.2 Adjust the wet gas flowmeter to a water-like state. Open the overflow valve and add steam until it overflows. When it stops overflowing, close the overflow valve.
C2.3 Open the air inlet valve, let in the raw gas, and use the regulating valve to adjust the gas volume. Note the starting reading of the wet gas flowmeter and start the stopwatch at the same time. When the gas volume of the through-type gas flowmeter is V, stop the stopwatch immediately; if the time is not exactly 1 minute, it is necessary to adjust the air intake until the gas volume passing through 1 minute is V. After repeating the measurement once, mark the position on the flowmeter to be calibrated. This position indicates the gas flow calibrated under the current conditions. During normal testing, the gas flow is based on this position. Additional notes:
This standard is prepared by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard is under the technical jurisdiction of the Research Institute of Nanjing Chemical Industry (Group) Corporation. This standard was drafted by Sichuan Chemical General Plant. The main drafters of this standard are Xu Qinghuai, Li Feiyu, He Shibing, Li Yun, Jing Gang, 10
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