HG/T 3544-1989 Test method for medium temperature shift catalyst of carbon monoxide
Some standard content:
Professional Standard of the People's Republic of China
Test Methods of High Temperature Carbon Anoxide Shift Catalyst1 Subject Insert and Scope of Application
ZB G74001-89
13744-1f8
Adjusted to: HG
This standard specifies the test methods for the activity, radial crushing strength, density loss rate, bulk alkali content, weight loss and chemical composition of the carbon monoxide medium temperature shift catalyst.
This standard is applicable to B107, B107-1, B108, B109, B110-2, B111 and 3112 carbon monoxide medium temperature shift catalysts for hydrogen production from carbon fluoride steam in ammonia synthesis and hydrogen production equipment. 2 Reference standards
Method for determination of crushing strength of fertilizer storage agent, molecular sieve and adsorbent particles An 33635
Method for determination of abrasion rate of fertilizer storage agent, molecular sieve and adsorbent G33636
GB6803
Test sieve
2B G 75501
ZBG75003
HG 1-1316
HG1-1427
3 Activity control
Analysis method of micro-bacteria of chemical secondary agent
Analysis method of blue loss by burning of chemical waist
1302 zinc oxide desulfurizer
Medium temperature shift catalyst chemical component analysis method3.1 Activity detection principle
Carbon monochloride in raw gas and a certain proportion of water vapor generate magnetic dioxide and hydrogen under the action of medium temperature shift catalyst. Its chemical reaction formula is as follows,
CO + H,0 = CO2 + 2
41.198 KJ/00!
3.2 Activity detection conditions
Reactor, this standard adopts a three-tube reaction group, and a single-tube reaction with the same tube diameter can also be adopted, and its tube diameter is 18×2. Catalyst loading, 5.00ml
Catalyst particle size: 1.40~2.00mm
Activity: 350±0.5℃
Heat-resistant temperature: 530±0.5℃
Space velocity, 2000±5h
System pressure, normal pressure
B111 type 400±0.5℃
Heat-resistant time, 15h
The ratio of water vapor to raw gas is 1.00±0.83. The raw gas is semi-water gas generated by indirect gas generation. Its composition is 21~32% (volume) of oxygen, 6~10% (volume) of carbon dioxide, 38~42 (volume) of hydrogen, 8.5% (volume) of oxygen and the rest are inert gases. Ministry of Chemical Industry of the People's Republic of China Issued on March 9, 1989 Sold on December 1, 1989
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3.3 Comprehensive test process
3.3.1 After the catalyst sample is crushed, it is sieved with a double test sieve with a pore size of 1.40~9.00. 10 ml of the sample is densely packed with 10% 1 weight and weighed to obtain the bulk density. Then weigh a sample equivalent to 5 double 1 mass 6
three-tube reactor cross-section
schematic diagram of carbon monoxide medium-temperature shift catalyst activity test device 1-4, 1-5, 1-6 valves, 2 pressure gauges, 3 oil-water separators, 4-1, 4-2, 4-3 silica gel, activated carbon, molecular sieve catalyzers, 1-1 1-2
4-4 filters, 5.16 thermocouple control sleeves, 6.15 electric heating furnace, 7.18 thermocouple splash temperature sleeves, 8 demagnetization furnace, 9-1, 9-2 rotor flowmeters, 10 Fuyong bottle, 11 temperature sensor, 12 precision thermometer 13 saturator, 14 insulation tube, 11 three-tube reactor, 19 cooling and avoiding steam-water separator, 20 venting bottle, 21 conversion gas sampling cock, 22 raw gas sampling, 23 cooling divider, 24 venting. 3.3.2 First place a layer of clean fine mesh at the bottom of the reaction tube. Then insert clean glass balls or quartz sand (2-3 cm in diameter), gently tap the wall of the reactor while filling, make the filling dense, and adjust the filling height until it reaches the specified size. Place another layer of copper mesh on the surface of the glass balls. Then slowly put some samples into the reactor, tap the wall to make the surface of the catalyst sample flat, and then place a layer of steel mesh, measure the highest catalyst filling height, and then install the glass balls or quartz sand to the reactor mouth, seal it with a pot net, tighten the reactor nut, and connect it to the system after testing that there is no air leakage at each joint in the system before testing. ZB G 74001-89
3.3.3 Insert the thermocouple into the thermocouple sleeve, so that it is inserted into the plane equivalent to the gas inlet end of the catalyst bottle bed layer. And the reactor, saturator, insulation tube, and desulfurization furnace are heated (the desulfurization furnace is not opened for the 111 type tester). The newly used desulfurizer should be heated and reduced in advance. The reduction method refers to the 3.1.4 clause of issue 1-1316. 3.3.4 When the desulfurization furnace temperature rises to 220℃, the saturator temperature rises by 2℃, the insulation tube temperature rises to 124℃, and the reactor temperature rises to 200℃, the source gas with a steam-gas ratio of 1.0 (space velocity 20) is introduced into the system to reduce the catalyst. The reactor temperature continues to rise to 530℃ and heat for 15h and then release to 350℃. The rise and fall rates are listed in Table 1. Table 1
Room temperature-200
200-530
530-531
530-350
Ramp rate
/hour
Ramp rate
Raise to 0℃ and start introducing raw gas with a steam/gas ratio of 1.5% reduction
Analyze after stabilization for three hours
3.3.5 After the catalyst is heat-resistant, reduce the reaction temperature to 350℃. After the air and saturator temperature are stable for 1 hour, it can be analyzed. Analyze the -1 short catalytic converter in the inlet and outlet gas every 1.0-1.5h. And calculate its conversion rate. Analyze three times in a row. If the difference in conversion rate is not less than 0.5%, it is considered that the analysis is stable and the furnace can be stopped. 3.3.6 When stopping the furnace, first cut off all power supplies in the system, drain the condensate in the condensate collector, and then shut off the gas. Then turn off the air intake cock and cooling water on the empty bottle.
3.3.7 Carbon monoxide conversion rate is calculated according to formula (1) E=
In the formula, E
Yro -- Vito
Vco (1+Vco)
Carbon monoxide conversion rate (expressed as percentage); -Volume percentage of carbon monoxide in raw gas: volume percentage of carbon monoxide in conversion gas. 3.4 Activity detection process
The process of the activity detection device is shown in Figure 1.
Determination of radial crushing strength of particles,
Strength determination method
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The method for determining the radial crushing strength of particles shall be tested in accordance with the provisions of GB3635. 4.2 Period of strength determination
The number of catalyst particles for radial compressive strength determination before reduction shall not be less than the known particles, which shall be directly selected from the experimental samples. 4.1 Calculation of radial crushing strength of chemical particles 4.3.1 The radial crushing strength of the ith particle is calculated according to formula (2): Pi
wherein, Pi
the radial crushing strength of the ith particle, N/c1
the radial compressive strength,
the length of the ith particle, C
4. 3.2 The average radial crushing strength of chemical particles is calculated according to formula (3): P
wherein, P" is the average radial crushing strength of the shear particles, Nc; the number of particles in the sample;
Pi the radial crushing strength of the ith particle, Nvc; 4.3.3 Calculation of the first fraction of low-strength particles
the percentage of strength is calculated according to formula (4):
wherein, --
percentage of low-strength particles;
—number of particles in the sample;
n—number of particles in the sample with radial compressive strength lower than 147N/c*. Determination of wear rate
determination method of wear rate
For the determination method of wear rate, refer to the provisions of GB3635. The specifications of the grinding sample selected in this standard are 50×300, 40.±29, and the sieve with a pore size of 2 that meets the requirements of GB6103-85 "Test Sieve" is used for sieving before and after grinding. 5.2 The grinding rate is calculated according to (5).
specified in (2). The sample volume is replaced by
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wherein,
abrasion rate, expressed as a percentage;
weighing bottle volume, 9 1
stomach,- weighing bottle plus the sample on the sieve before grinding, 9, weighing bottle plus the sample on the sieve after sieving, 9. 5.3 The average wear rate is calculated according to formula (6)
a,+ a?
In the formula, X
is the average wear rate, expressed as a percentage; -2——is the wear measured in two parallel measurements, 5.4 allowable error
parallel measurement relative error shall not exceed 11 of the average value. Determination method of ignition loss
For the determination method of ignition loss, please refer to the provisions in 23G75003. This standard adopts the original base of the oxidizer to determine the ignition loss after ignition at 600℃ for 2h.
Ignition loss is calculated according to formula (7)
Where, X
Ignition loss, expressed as a percentage;
ignition sample and Yaoding weight, 9;
after ignition sample and added crucible. 9
Sample mass, sub.
7 Analysis of main chemical components
7.1 Analysis of iron oxide and oxidative complex in the chemical shall comply with the provisions of 3 and 4 of G1-1427. 7.2 Analysis of bulk sulfur content in chemical products shall comply with the provisions of ZBG751. 1.3 Determination of total phase content
7.3.1 Principle of the method
In an acidic medium, hexavalent ascorbic acid is used to reduce pentavalent molybdenum. Pentavalent molybdenum forms a blood-red complex with alkaline cyanate. The higher the pentavalent molybdenum content, the darker the color of the complex. The absorbance of the solution is measured by spectrophotometry, and the corresponding molybdenum content is found from the standard curve, from which the molybdenum content in the sample is calculated. Trivalent iron forms a red complex with alkaline cyanate. After adding a reducing agent, the reduction of trivalent iron to divalent iron no longer affects the determination. The presence of a certain amount of iron can make the color development complete quickly and help molybdenum maintain a pentavalent state. The sensitivity of this method is 7.5+g/5l. 7.3.2 Preparation of reagents and solutions
7.3.2.1 Sulfuric acid (GB625)
7.3.2.2 Magnesium (GB625), (1+1)
7.3.2.3
Acid (GB25), (1+100)
Carbonic acid (B625) (1+3)
7,3.2.5 (GB1282).
ZBG74001-89
Main, mix 1 volume of nicotinic acid (GB626) and 3 volumes of hydrochloric acid (B622). 7.3.2.2 Sodium ferric sulfate (CB629), 4g<1%>, 50g
7.3. 2.22
7.3. 2. Ammonium ferric sulfate (GB1279). 59-L Prepared by diluting equal volumes of (1+9) oxalic acid and (1+]) phosphoric acid. 1.3.2.19 (B624). bzxZ.net
7.3.2.11 Aluminum trioxide, 50μgl standard solution. Heat the molten acid (7.3.2.1030.0500g) that has been burned at 500~-520℃ for 1h in a beaker and dissolve it with 5-well hydroxide solution (7.3.2.7). 31 Figure 1 (1+3) Magnetic acid (7.3.2.4), transfer it to a 1000 value bottle, dilute it to the scale with distilled water, and insert it evenly. 7.3.2.12 Ammonium (669) 100g 1
7.3.3 Commonly used test samples Prepare
Take out about 20g of the sample, grind it in a grinder, make it all pass through a 125u test sieve (to be in accordance with the aperture size of GB6003R40/series), put it into the sieve, and store it in a dryer for chemical component analysis. 7.3.4 Effective
Test room - Fusion technology data and
Spectrophotometer
7.3.5 Standard drawing
Take 52 bowls of ammonium ferric ( 7.3.2.9) 5 parts, the amount of five 501 volumetric flasks, respectively add 0, 1, 2, 3, 4, blue oxide reading clear liquid (7.3.2.11) and then add 10 free mercapto acid solution (7.3.2.12), 12 (1 + 3) alkaline acid (7.3.2.42, 10ml ascorbic acid solution. 3.2.83, dilute with distilled water to degree, shake well, let stand for 20 minutes, use a spectrophotometer at 470m At 1000 nm, use 2C colorimetric and white roller for quaternization, measure the absorbance of the standard series one by one, and draw a standard curve. 7.3.6 Determination of the content of the standard
recommended by the manufacturer), 2003g of the standard is placed in a 258ml beaker, add 20ml aqua regia (7.3.2.6) and 101 acid (7.3.2.5) and heat to dissolve, then add 20+1) magnetic acid solution (7.3.2.2) and evaporate until the acid is broken, take out the beaker and cool. Add a small amount of water to dissolve the salt. Filter with qualitative filter paper and place in a 20ml volumetric flask. Wash the filter paper in the beaker with (1+100) sulfuric acid (7.3.2.3) for 5-6 times, add the liquid into the container, dilute to the scale with distilled water, and take. Take 5 ml of the solution and place it in a 50ml sensitive bottle, add 12 ml (1+3) sulfur (7.3.2.4), 10 ml ammonium thiourea solution (7.3. 3.12), and 10 ml ascorbic acid (7.3.2,8) solution. Mix each reagent evenly, and finally dilute to the scale with distilled water, shake, and mix. Mix it with the standard series in opposite instruments and measure the absorbance of the sample solution under the conditions. The corresponding potassium trioxide content can be obtained from the standard curve, and the percentage of potassium trioxide can be calculated by formula (8): $x16
In the formula. The percentage of potassium trioxide can be obtained from the standard curve. The potassium trioxide content is the same as the quality, 9
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Determination of health and medical isothermal zones
(reference)
A1 In order to detect the activity of the skin-degrading agent, the chemical must be installed in the isothermal zone of the reactor. Therefore, for newly manufactured or newly replaced electric furnaces, the isothermal zone of the reactor must be measured. A2 Fill the reactor tube with glass balls, align the reactor pipe mouth, tighten the reactor screws, and connect the reactor to the activity detection installation process. After everything is ready, start heating,
A3 Raise the temperature of the desulfurization furnace to 220℃ and keep it constant; raise the humidity of the heating furnace to 82C and keep it constant; raise the temperature of the insulation pipe to 120℃ and keep it constant. The heating rate of the furnace is about 9℃h. When its temperature rises to 200℃, a steam/gas ratio of 1 is introduced into the activity detection device system. ,0 of raw gas (make the float of the glass rotor flowmeter at 200 empty). When the temperature of the reactor rises to 350℃, start measuring the equal coverage area after the temperature stabilizes for two hours. A4 Record the length of the thermocouple inserted into the thermoelectric regulating sleeve and the corresponding temperature, and record the temperature at the origin. First insert the thermocouple into the thermoelectric network sleeve, wait for about one minute for every 10cm inserted, and record the temperature after stabilization, until the temperature difference is more than 2℃ after the thermocouple is inserted 1. Then pull the thermocouple out, wait for about one minute for every 1cm pulled out, and record the overflow after stabilization, until the temperature difference is more than 2℃ when the thermocouple is pulled out. Then insert the thermocouple into the thermocouple sleeve again, using the same method as above. The measurement is completed until the thermocouple is inserted to the origin.
A5 Repeat the measurement according to the method of A4. Once, take the common isothermal zone determined twice as the isothermal zone under this temperature. A6 Raise the furnace temperature to 530℃, stabilize for 2h, and then determine the isothermal zone at 530℃ according to the methods of A4 and A5. Take the common isothermal zone of 350℃ and 536℃ as the isothermal zone of this reaction. A7 Sometimes the measured temperature does not show the isothermal zone. The reactor needs to be dismantled, the density position of the electric furnace wire is adjusted, and then the isothermal zone is re-measured. Make the temperature difference in the isothermal zone no more than 1℃, and the length of the isothermal zone is greater than 45. A8 According to the length of the isothermal zone, determine the depth of the glass balls at the bottom of the reaction tube and the filling position of the catalyst, and calculate the length of the thermocouple insertion.
Water vapor
2BG74001-89
The ratio of water vapor to raw gas is low, which is a problem for a test tube. The chemical magnetic conversion rate has a great influence, and a certain range of
is required.
Measurement process
Measurement equipment is shown in Figure B1.
Measurement equipment for the ratio of water vapor to raw gas
1. Mixed gas of raw gas and water vapor; 2. Condenser; 3. Cold splash pipe collector, 4. Water-filled pressure gauge; 5. Thermometer: 6. Wet gas meter; 7. Vent B1.2 Heat the saturator to 92°C, introduce raw gas into the device, and introduce cooling water into the condenser. After the saturated temperature stabilizes for 1 hour, release the cooling water in the condensate collector, and record the initial reading of the wet gas flow meter, and continue to let the raw gas pass through the saturator into the wet gas flow meter. When the condensate in the condensate collector reaches a certain value (water), net raw gas. Record the volume of gas passing through the wet flowmeter (Y,>. Record the atmospheric pressure of the chamber and the reading of the water pressure gauge on the condensing flowmeter. B2 Calculation of the ratio of water vapor to source gas
B2. 1 The water vapor volume Y, corresponding to the raw gas volume V, is calculated according to formula (B1). V,=V* ×Dt+
The volume of raw gas passing through the wet gas flowmeter, 1Wherein, V,
The volume of condensed water, al
The volume of water vapor corresponding to the volume of raw gas, 1Yz
The density of water at room temperature t, 9/B1
The number of grams of water vapor contained in each cubic meter of raw gas at the measured overflow, 9/The volume of water vapor corresponding to 1g of condensed water, (/g. B2.2 The ratio of water vapor to raw gas is calculated according to the formulaCalculate the steam volume
where t,-
where Po-
273—
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The steam volume corresponding to the raw gas volume, 11(B2)
The raw gas volume passing through the bypass gas flowmeter, 1The conversion factor for converting the raw gas volume to the volume under standard conditions at the measuring temperature is calculated according to formula (B3),, =
P+P, P2
Atmospheric pressure under standard conditions, Pa:
Maximum pressure during measurement, Pa ;
The pressure of the rotor flowmeter, Pa: The partial pressure of water vapor at the temperature t of the rotor flowmeter, Pa The temperature when the measurement is, ℃1
Absolute degree, area
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Reference)
The size of the gas flow directly affects the activity of the catalyst, so if the room changes greatly or the activity reverses, the rotor flowmeter should be corrected. The correction method can be the evaporation gas flowmeter measurement method or the soap bubble measurement method. Cr
Thermostatic flowmeter measurement method
Connect the mixed gas meter and the rotor flowmeter according to Figure E1 Figure C1 Gas flowmeter measurement method 1. Raw gas inlet; 2. Gas volume adjustment: 3. Rotor gas flowmeter: 4. Mercury pressure gauge: 5. Mercury thermometer, 6. Hydration gas flowmeter: 7. Bubble. First, adjust the level of the condensing gas flowmeter. Then open the cock of the water level overflow hole, add distilled water into the condensing gas flowmeter, and when water seeps out of the overflow hole, stop adding water, and when the overflow hole is no longer flooded, close the cock of the overflow hole. C1.2 According to the amount of chemical and the active space velocity, calculate the gas flow rate Vo under standard conditions according to formula (C1). Yoa
In the formula, sy-
space velocity, h;
amount of chemical, ml
gas flow rate under standard conditions, /min. E1.3 Convert the flow rate Yo under standard conditions to the gas flow rate V under the current conditions, and calculate PcYo
according to formula (E2) where Po -
- atmospheric pressure under standard conditions, Pa
atmospheric pressure during measurement, Pa;
- temperature under standard conditions, 273k1
- temperature during measurement, (=Ta+room temperature);
- gas flow rate during measurement, lnin.
C1.4 Record the initial reading of the wet gas flowmeter, open cock 1, and allow the raw gas to enter the diffuse gas flowmeter through the rotor gas flowmeter for measurement, use cock 2 to measure the gas volume, and start the stopwatch. When the gas passing through the diffuse gas flowmeter in one minute is equal to , mark the scale mark on the upper end face of the rotor gas flowmeter. And then measure the short time, determine the scale position of the upper end of the float to calibrate the pregnant body flow.
Heart 2 Bubble culture most measurement method
I quickly as far as possible is the corresponding
through glass tube and then install the clean nipple, and connect according to Figure C2 C2.1
Connect the lower end of the 50ml alkaline burette to the three
rubber head and twist
help soap liquid to the lower end of the gas inlet of the three-way glass tube) Figure 62 Bubble flowmeter measurement method pull correction device 1. Raw gas cock: 2. Gas disc steel cock; 3. Rotor gas flowmeter; 4. Soap bubble flow disc meter, 5. Bracket; 6. Vent. C2.2 Open cock 1, let the material gas pass into the rotor flowmeter (the float rises at this time), enter the alkaline burette, use cock 2 to adjust the size of the flowmeter (the float in the rotor flowmeter rises and falls accordingly), and gently pinch the latex head with your hand, and the soap film will rise with the gas. When the soap bubble reaches a certain scale, start the stopwatch at the same time and write down the starting scale. When the soap bubble film reaches another appropriate scale position, press the stopwatch, write down the time and the end scale reached by the bubble film on the alkaline burette, and calculate whether the gas flow rate per minute is Y. Adjust the flowmeter and repeat the measurement until the gas flow rate is V. Write down the scale position corresponding to the upper end face of the float in the rotor flowmeter at this time. This position is the corrected gas flow rate.
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The bulk density of the chemical is an important reference for the design of the reactor and the understanding of the chemical environment
D1.! Use a test sieve with an aperture of 2.00 to sieve out the chemical dust, and slowly add the sample into a 1000L measuring cylinder at a speed of about 50l/s. When the amount of the initial sample is close to 1000L, add the chemical sample one by one to 1000L. D1.2 Weigh the mass of the 1000L measuring cylinder and the 100L sample in the cylinder, and weigh to 1g. D2 Observation of bulk density
02.1 Divide the sample on the sieve into five portions, each portion is about 200 liters, and add them into a 1000m3 measuring cylinder in sequence. Each time, the cylinder must be moved up and down several times until the position of the sample in the cylinder remains unchanged. The total weight of the sample is 1 liter. 02.2 Weigh the weight of the sample and the weight after weighing, and weigh to 19. D3 Calculation of bulk density
.1 Bulk density (loose bulk density or bulk density) is calculated according to formula (D1). p
In the formula: p
Loose bulk density or bulk density, kg: 1 The mass of the measuring cylinder, kg
The mass of 1000m1 of the measuring cylinder plus 1000m3! The total weight of the sample is kg, and the total weight of the sample is L(1001).
D3.2 Take the average value of the two measurements as the measurement result. The relative error between the two measurements shall not exceed 2.0%.
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