Some standard content:
Chemical Industry Standard of the People's Republic of China
Test Methods for Organic Sulfur Hydrogenation Catalysts
1 Subject Content and Scope of Application
HG / T 2514
This standard specifies the test methods for the activity, crushing resistance, attrition rate and bulk density of organic sulfur hydrogenation catalysts. This standard is applicable to T201.T (T) 203 organic sulfur hydrogenation catalysts used in synthetic ammonia, synthetic methanol and hydrogen production equipment. The tests of other organic sulfur hydrogenation catalysts with alumina as carrier and cobalt and molybdenum as active components can also be used for reference. 2 Reference standards
GB/T3635 Determination method for crushing resistance of target catalysts, molecular sieves and adsorbent particles GB/T3636 Determination method for attrition rate of fertilizer catalysts, molecular sieves and adsorbents GBLT9722 Chemical reagent gas phase chromatograph..
3 Activity determination method
Clearance detection principle
Organic sulfide can be converted into hydrogen sulfide under the action of the added catalyst. Taking the most difficult to convert phenanthroline as an example, its hydrogenation reaction such as CHS+4H--,H+Hs
4H*--280 3.kl · moll
Under certain experimental conditions, the conversion rate of the sample to phenanthroline is determined. 3.2 Experimental equipment and instruments
3.2.1 Gas chromatograph Any type of gas chromatograph with a thermal conductivity detector, its sensitivity and stability should comply with the relevant provisions of GB/T9722.
3.2.2 Reactor specifications: (inner diameter × length) 6.mm × 50mm3.23 Heating power: ≥1500W.bzxZ.net
3,2 Fine chain temperature controller control accuracy: 1250±0.5℃,:32 Thermal liquid indexing instrument accuracy level: 1.0 level,32.8 Yongyinmeng temperature meter 0~500℃.
3.2.7 Thermoelectric precision
3.2.8 Micro syringe 0~10μL.
3.2.9 Volume 5mL.
3.2.10 Test sieve 250~425μm (in accordance with GB6003, R40/3 series). 3.3 Reagents and materials
3.3.1 Anthotane, gas chromatography stationary liquid. 3.3.2 Ether (GB/T12591)
Analytically pure.
3.3.3 Thiophane: chemically pure.
Ministry of Chemical Industry of the People's Republic of China: Approved on September 9, 1993, implemented on July 1, 1994
3.3.4 Hexane: high purity.
HG/T 2514 — 93
3.3.3, bottom vegetable carbonyl separation purity.
3.3.6·101 self-chromatographic support, chromatographic support, 250.~180um.3.3.7 Sodium nitrate (GB:/T636) chemically pure.3.3.8 Potassium nitrate (GB/T647) chemically pure.3.3.9, Sodium nitrite (GB/T633) chemically pure. 3.3.10° Quartz sand particle size 850~425um. 3.3.11 Hydrogen purity is 99.99%,
3.4 Activity test See Figure: 1
Figure 1 Organic sulfur padded catalyst plug test process Figure 1 Hydrogen cylinder: 2
2-Hydrogen alkali pressure gauge; 3--Gas purifier: 4-~ Deoxidizer: 5-Dryer: 6--Chromatograph flowmeter; 7-Chromatograph pressure gauge: 8-Injector: 9-Chromatograph 10-Calling: 11-Reactor; 12-Heating furnace 3.5 Activity test conditions
3.5.1 Catalyst loading 0.7mL, particle size 250~425um, 3.5.2 Pressure, normal pressure,
3.5.3 Reaction temperature 350±1℃.
3.5.4. The test solution is a mixture of hexane and n-hexane, with the ratio of hexane to n-hexane being 1. Hydrogen is used as the oxygen source and chromatographic carrier gas 3.5.5: Chromatographic conditions
3.5.5.1 Column temperature 75±2;
Regulator overflow 75±2:
3.5.5.2 Gas flow rate. 100mL/min (hydrogen is the carrier gas). 35.5.3 Vaporization temperature: 100~110℃,
3.5.5.4 Bridge current 150mA,
3.5.5.5 Chromatographic column @5×1mm, column length 2m, column head pressure 0.1MPa: 3.5-5.6. Recorder sensitivity 5-mV
36% Test position: 21
3,6. Sample preparation
HG:/ T 2$14 -93
Take out about 10 catalysts from the laboratory sample by quartering method. After being crushed into 250~425jμm, freeze at 120℃ for 1h, cool to room temperature in a desiccator, use a 5mL measuring cylinder to tightly stack 2mL of sample and weigh it to obtain the bulk density, and then weigh the sample equivalent to 0.7mL of mass.
3.6.2 Catalyst loading
Put the 0.5mL cleaned flask into the reactor with a small piece of chrome wire mesh at the bottom of the reactor, and then pour the 0:7m sample into the reactor, gently hitting the reactor wall while pouring. After the sample is filled, add quartz sand to the upper part of the reactor until it is 5mm away from the upper mouth. Connect the reactor to the system and test it with carrier gas. Only after the system leak test is qualified can the test be carried out. 3.6.3.. Catalyst presulfurization
After passing the gas, start the chromatograph, recorder and heating furnace. When the salt bath is heated to about 300℃, connect the reactor to the system. After the reaction temperature reaches 350±1℃ and stabilizes, pass the gas into the reactor. When the flow is stable, presulfurization can be carried out. 3μL carbon disulfide is injected every 2min, and a total of 10 pulses are injected. 3.6.4 Activity determination
After the catalyst is presulfurized and stabilized for 10 minutes, pulse injection of thiophene n-hexane solution is performed for activity test. 2L thiophene n-hexane solution is injected into the reactor every 2 minutes, and a total of 10 pulses are injected. The peak height of unreacted thiophene after each pulse injection is measured. Then the four valves are switched so that the carrier gas does not flow through the reactor, and 5 pulse samples are injected to measure the peak height of thiophene before the reaction. The average value of the peak height measured at least 3 times before the reaction is taken as the measurement result, and the average value of the peak height measured at least 7 times after the reaction is taken as the measurement result. The absolute difference of the data taken is 5m. Calculate the conversion rate of pyrolysis according to the formula (): A
Where: A——pyrolysis conversion rate, %;
A——average peak height of pyrolysis before reaction, mm; average peak height of pyrolysis after reaction, mm
After the test, cut off the power supply, remove the reaction tube, and turn off the carrier gas after 10 min. 4 Determination of radial crushing strength of particles
The determination and calculation of radial crushing strength of particles shall be carried out in accordance with the relevant provisions of GB/T3635. 4.1 Tester
Range: 0～250 N
Accuracy: Class 1
Force speed: 5N/s
4.2 Particles for strength determination
Randomly select 50 pyrolysis samples from the flower sample, cut them to a length of 4～6mm, grind both ends flat, and measure the crushing strength of each particle.
5 Wear test
The wear rate shall be measured and calculated in accordance with the relevant provisions of GB/T3636. 5.1 Determination system
Speed: 25±1mm
Number of revolutions: 500 rpm
Grinding sample size (inner diameter × length: 36mm × 300mm) Sample loading: 25±2.2. Precision: 0.01g3
HG/T 2514-93
The sample shall be ground before and after grinding with a material that complies with GB 6003 R40/3 series, sieve with a 2.00mm aperture; weigh and record: 6 Determination of density of flower initiator
The bulk density of the catalyst is an important parameter for reactor design and catalyst loading. 6.1. Use a test sieve with a 2.00mm aperture to screen the catalyst powder. Divide the sample after olefination into 5 portions, each about 200mL: add 1000mL of liquid, and add it up and down. When the amount of added sample is close to 1000mL, add it one by one until the scale is reached.
6.2. Weigh the mass of the 1000mL sample and the 1000L measuring cylinder after weighing, and guess it to 1g. 6.3. The bulk density is calculated according to (2). Y
Wu Zhong: p-
- Catalyst bulk density, industry gL:
000 plate mass
.m21000mL volume mass plus 1000.mL sample mass, sample volume: (1.000mL):
6.4 Take the average of the two measurements as the measurement result, and the relative error is not greater than 2% (2)
A1 Interesting scroll!
HG/T 2514-93
Preparation of chromatographic columns
(Supplementary)
Accurately weigh 3g of oxadiazine and dissolve it in 65m ether: after it is completely dissolved, pour it into 60g of 10l white support in evaporating water, gently stir it, and dry it at 50°C for later use. A2 Filling method
After washing and drying the inside of the column, fill a small amount of glass wool at the outlet of the column, wrap it with gauze and connect it to the vacuum pump, then Then, the stationary phase is loaded from the other end of the column tube. During the loading process, the column tube should be gently tapped. After it is filled, an appropriate amount of glass wool is added. The chromatographic column should be filled tightly and evenly. 3. Aging of the chromatographic column. Connect one end of the loaded chromatographic column to the gas path of the chromatograph, and do not connect the other end to the identifier for the time being. Introduce gas, gradually increase the column temperature to 100℃, and age it for 4~8h at a gas flow rate of 50mL/min. Appendix Preparation of salt bath (reference) B1 The mixed salt formula is NaNO, 7%, KNO, 53%, NaNO2 40% B2. After fully mixing the above three salts, add them into the stainless steel salt bath. After slowly heating to 200℃, the mixed salt begins to melt, and continue to add the mixed salt at this temperature until the pre-screw at the inlet of the reactor is buried. The maximum operating temperature shall not be higher than 500℃. Strictly, water dripping into the reactor will cause boiling and agglomeration. C
Reactor temperature control and determination of salt bath isothermal zone: (reference material!
C1. Reactor temperature control
The reactor temperature control adopts chromium-silicon thermocouple and density controller. C2 Determination of salt bath isothermal zone
When determining the activity of organic sulfur hydrogenation catalyst, the reactor must be installed in the isothermal zone of the salt bath. Therefore, the isothermal zone of the salt bath should be measured first. The measurement steps are as follows:
Insert the thermocouple into the bottom of the salt bath tube, start the heating furnace, and gradually raise the salt bath temperature to 350C. After stabilization for min, record the length of the thermocouple and the corresponding temperature, that is, the temperature at the origin: Then pull the thermocouple out; every time it is pulled out 20mm, record the temperature is isothermally: pull the thermocouple out 20mm, until the temperature is above 2, then insert the thermocouple into the salt bath, until the thermocouple reaches the origin, the measurement is completed. C3 Repeat the measurement once according to the method of ℃2, and take the isothermal zone at the core temperature where the temperature difference between the two measurements is not less than 1.
C4 According to the length of the zone, determine the filling position of the reactor, and calculate the length of the thermocouple insertion, HG / T: 2514 93 :
More stable than the sub-flow measurement
(reference
The size of the gas flow directly affects the activity of the catalyst, so when the room temperature changes greatly or the activity shows abnormal phenomena, the flow of the rotor meter must be calibrated: The calibration method is the bubble flow measurement method: D1 Connect the lower end of the 25mL alkaline burette to the three-way glass tube, and then install the clean latex head and connect according to Figure; D. (Add dilute soap solution to the lower end of the three-way glass tube gas inlet), Figure D Soap bubble flow Meter calibration device
[1-hydrogen cock: 2-gas volume adjustment cock; 3-rotor gas flowmeter; 4-soap bubble flowmeter: 5-channel D2 Open cock 1 to allow oxygen to quickly enter the rotor flowmeter. At this time, the float rises and the gas enters the alkaline burette. Use cock 2 to adjust the size of the flowmeter (the float in the rotor flow rises and falls accordingly). Gently pinch the latex head with your hand, and soap bubbles will rise with the gas. When the soap bubbles reach a certain scale, start the stopwatch and record the starting scale. When the soap bubbles reach another appropriate scale. Press the stopwatch, record the time and the end scale that the soap bubbles reach on the alkaline burette: and calculate whether the gas flow rate per minute is V. (V is the gas flow rate under standard conditions), adjust the flow rate, repeat the measurement until the gas flow rate is Vo, and record the scale position corresponding to the surface of the float in the rotor flowmeter at this time. The flow rate at this position is the gas flow rate under the calibrated working condition. Additional Notes:
This standard was issued by the Science and Technology Department of the Ministry of Chemical Industry of the People's Republic of China. This standard was drafted by the Nanjing Chemical Industry (Group) Research Institute. This standard was drafted by the Fertilizer Industry Research Institute of the Ministry of Chemical Industry. The main drafters of this standard are Niu Zhi, Hong Xu, Ma Kui, Tongpin
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