CN113960150B - Method for eliminating measurement deviation caused by residual air of micro fluidized bed reaction analysis instrument - Google Patents
Method for eliminating measurement deviation caused by residual air of micro fluidized bed reaction analysis instrument Download PDFInfo
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Abstract
A method for eliminating measurement deviation caused by residual air of a fluidized bed reaction analysis instrument relates to a method for eliminating measurement deviation of a micro fluidized bed reaction analysis instrument, which comprises the steps of firstly, arranging a path of protection gas at a micro fluidized bed reactor bypass, controlling the protection gas flow by a mass flowmeter, and removing residual air in a branch pipe of the reactor by switching fluidization carrier gas and the protection gas; then quartz sand is used as a fluidization medium to be filled into a micro fluidized bed reactor; and (3) introducing the protective gas into a branch pipe of the micro fluidized bed reactor filled with the sample to be detected, and monitoring the air content change on line through a process mass spectrum. The invention effectively eliminates the residual air in the branch pipe of the micro fluidized bed reactor, avoids the influence of the residual air in the branch pipe of the reactor on the relative content of the gas products with the same molecular weight measured by the process mass spectrum, and obtains accurate reaction dynamics data. The method is simple, has strong operability and more accurate measured data.
Description
Technical Field
The invention relates to a method for eliminating measurement deviation of a fluidized bed analysis instrument, in particular to a method for eliminating measurement deviation caused by residual air in a micro fluidized bed reaction analysis instrument.
Background
The gas-solid reaction is a common chemical reaction in the process engineering fields of chemistry, chemical engineering, metallurgy, environment, energy conversion, material science and the like, accurate reaction rate, reaction time and kinetic parameters are obtained, the gas-solid reaction is a basis for research and development in the process engineering fields, and mathematical models and necessary quantitative basis can be provided for amplification of laboratory research results and reactor design.
The micro fluidized bed reaction analyzer is a new instrument complementary to the thermogravimetric analyzer and is generally composed of four parts: an electric heating furnace, a micro fluidized bed reactor made of quartz glass and having a diameter of 20 mm, a sample pulse injection system and an on-line process mass spectrum. The analyzer has the advantages of fast heat and mass transfer, minimized external diffusion inhibition, uniform temperature and reactant concentration distribution in the axial direction and the radial direction, fast feeding by using a small amount of sample particles, fast on-line analysis of gas products and the like, and is successfully applied to research on various mechanisms and dynamics of gas-solid reaction, mainly comprising oxidation reduction, hydrogenation and the like of chemical substances in chemical industry, decomposition, combustion of solid wastes in environment, absorption, adsorption and the like of waste gas, roasting and reduction of ores in metallurgy, such as roasting of sulfides, and strong exothermic reactions such as explosion, explosive decomposition and the like in the field of materials.
The time-dependent change in the content of the gas product measured by the micro-fluidized bed reaction analyzer can be used to calculate the reaction kinetics, since the on-line process mass spectrum can only distinguish between gases of different molecular weights, while it is difficult to distinguish the components of gases having the same molecular weight. During pulse sample injection, residual air in the branch pipe of the reactor can enter the reactor along with the sample, so that a certain amount of air, mainly nitrogen (with a molecular weight of 28) and oxygen (with a molecular weight of 32), is contained in the gas product, and the content of the gas products (such as CO, methanol, ethylene gas and the like) with the molecular weights of 28 and 32, which are measured by on-line process mass spectrometry, has a certain error, deviates from an actual result, and causes a certain deviation of a calculated dynamic result.
Disclosure of Invention
The invention aims to provide a method for eliminating measurement deviation caused by residual air of a micro fluidized bed reaction analysis instrument, which is simple and convenient in design due to the fact that protective gas is arranged on the micro fluidized bed reaction analysis instrument. The protective gas flow is controlled by a mass flowmeter, so that the influence of residual air of the branch pipe of the micro fluidized bed reactor on the measured relative content of the gas product is eliminated, the reaction rate and the reaction dynamics are accurately measured according to the concentration change of the gas product, and the deviation of the measurement result is eliminated.
The invention aims at realizing the following technical scheme:
firstly, filling a proper amount of quartz sand into a micro fluidized bed reactor, heating the reactor to a preset temperature, and after the temperature reaches the preset temperature, introducing carrier gas from the bottom of the micro fluidized bed reactor through a mass flowmeter to enable the quartz sand in the bed to be in a stable fluidization state, wherein the concentration of the carrier gas monitored by mass spectrum in an online process is stable and does not change any more, and closing the carrier gas;
weighing a certain amount of solid samples to be measured, loading the solid samples into a sample injector of a micro fluidized bed reactor branch pipe, then introducing protective gas into the micro fluidized bed reactor branch pipe filled with the samples to be measured through a mass flowmeter, and monitoring the air content change on line through a process mass spectrum;
introducing fluidizing carrier gas from the bottom of the micro fluidized bed reactor again to stabilize the monitored carrier gas concentration until no change occurs, closing the fluidizing carrier gas, then introducing protective gas into the branch pipe of the micro fluidized bed reactor, opening the fluidizing carrier gas again after a period of time, repeating the process for 2-3 times until the content of air in the branch pipe of the reactor is stabilized to be unchanged, indicating that residual air in the branch pipe is completely removed, and closing the protective gas;
introducing fluidizing carrier gas, when quartz sand in the bed reaches a stable fluidization state, rapidly pumping solid sample pulse to be detected into the micro fluidized bed reactor by controlling the electromagnetic valve, and calculating the dynamics of the reaction according to the relation of the relative content of the gas product monitored on line in the rapid process mass spectrum with time.
And the inlet of the mass flowmeter arranged in the micro fluidized bed reactor bypass system is connected with gas, and the outlet of the mass flowmeter is connected with the inlet of the micro fluidized bed reactor branch pipe.
The gas flow rate of the mass flowmeter arranged in the micro fluidized bed reactor bypass system is set on the premise that the standing state of the solid sample to be detected in the sample injector is not affected, for example, the gas flow rate is lower than 100 mL/min.
The protection gas introduced into the micro fluidized bed reactor bypass system is the same as the fluidization carrier gas introduced from the bottom.
The invention has the advantages and effects that:
the invention controls the protective gas flow by the mass flowmeter, and eliminates the residual air in the branch pipe of the reactor by switching the fluidization carrier gas and the protective gas, so that the influence of the residual air in the branch pipe of the reactor on the relative content of the gas product with the same molecular weight measured by the process mass spectrum is avoided when the gas product is monitored and analyzed in real time by the online process mass spectrum, the more accurate relative content of the gas product is obtained, and the accurate and reliable reaction kinetic parameters of the gas product in the gas-solid reaction are obtained. The method is simple, safe, effective, strong in operability, more accurate in obtained data and innovative.
Drawings
FIG. 1 is a schematic diagram of a micro-fluid bed reaction analyzer with a shielding gas in the bypass system of the micro-fluid bed reactor according to the present invention;
FIG. 2 is a graph showing the variation of nitrogen and oxygen contents with time as measured by mass spectrometry of the process between (a) complete elimination of residual air from a branch pipe of a micro-fluidized bed reactor at 450℃in an Ar atmosphere and (b) no elimination in example 1;
FIG. 3 is a gas product CO of the micro-scale fluidized bed reactor branch pipe residual air of example 2 monitored by mass spectrometry during the decomposition of siderite in Ar atmosphere at 450 ℃ with (a) and (b) without elimination 2 And the CO content over time.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The micro fluidized bed reaction analyzer comprises an electric heating furnace, a micro fluidized bed reactor made of quartz glass and having the diameter of 20 mm, a sample pulse injection system and an online process mass spectrum. Referring to the dashed box of fig. 1, a mass flow meter is provided in the micro fluidized bed reactor bypass system for introducing shielding gas, an inlet connected to the gas, and an outlet connected to the reactor manifold.
Firstly, quartz sand is used as a fluidization medium to be filled into a micro fluidized bed reactor, then the reactor is heated to a preset temperature, and after the preset temperature is reached, fluidization carrier gas is introduced from the bottom of the micro fluidized bed reactor until the concentration of the carrier gas monitored by mass spectrum in an online process is stable and does not change any more, and the fluidization carrier gas is closed at the moment;
weighing a solid sample to be measured, loading the solid sample into a sample injector of a branch pipe of the micro fluidized bed reactor, then introducing protective gas into the branch pipe of the micro fluidized bed reactor filled with the sample to be measured, and monitoring the air content change on line through a process mass spectrum;
introducing fluidizing carrier gas from the bottom of the micro fluidized bed reactor again to stabilize the monitored carrier gas concentration until no change occurs, closing the fluidizing carrier gas, then introducing protective gas into the branch pipe of the micro fluidized bed reactor, opening the fluidizing carrier gas again after a period of time, repeating the process for 2-3 times until the content of air in the branch pipe of the reactor is stabilized to be unchanged, indicating that residual air in the branch pipe is completely removed, and closing the protective gas;
introducing fluidizing carrier gas, when reaching a stable fluidization state, rapidly pumping the solid sample pulse to be detected into the micro fluidized bed reactor by controlling the electromagnetic valve, and calculating the dynamics of the reaction according to the relation of the relative content of the gas product monitored on line in the rapid process mass spectrum with the change of time.
Example 1
Taking pulse into empty material as an example, the specific embodiment of the invention is further described:
(1) Before the experiment, quartz sand with the mass of 3g and the particle size of 150-270um is taken as a fluidization medium to be filled into a micro fluidized bed reactor;
(2) After the micro fluidized bed reactor is heated to 450 ℃, introducing 400 mL/min of fluidization carrier gas (Ar) from the bottom of the reaction tube, and closing the fluidization carrier gas when the concentration of the carrier gas monitored by the mass spectrum of the online process is stable and does not change;
(3) By controlling a bypass mass flowmeter of the reactor system, introducing 70mL/min of protective gas (Ar) from a right branch pipe of the reaction pipe, and monitoring the air content change through a process mass spectrum after two minutes of introduction;
(4) Introducing fluidizing carrier gas from the bottom of the micro fluidized bed reactor again to stabilize the carrier gas concentration detected by the mass spectrum in the online process until no change occurs, and closing the fluidizing carrier gas;
(5) Then, after two minutes of protective gas is introduced into the branch pipe of the micro fluidized bed reactor, the fluidization carrier gas is opened again, and after the process is repeated for 2-3 times, the protective gas is closed;
(6) When the concentration of the carrier gas detected by the on-line process mass spectrum is stable, pulse empty materials in the reactor, monitor the air content change by the process mass spectrum, as shown in fig. 2 (a), compare with the air content generation curve of the pulse empty materials measured without eliminating the residual air of the branch pipe, as shown in fig. 2 (b), it can be seen that after eliminating the residual air of the branch pipe according to the methods (1) - (5), the air content in the branch pipe of the reactor is stable and has no change, and the residual air in the branch pipe is completely removed;
example 2
With siderite (FeCO as main constituent 3 ) The decomposition reaction process in an inert atmosphere (Ar) is exemplified by the thermal decomposition of siderite in an inert atmosphere with the main gaseous products of CO and CO 2 Further illustrating the embodiments of the invention:
repeating the operation steps (1) - (2) in the first embodiment, weighing about 20mg siderite sample, and loading into the injector of the micro fluidized bed reactor branch pipe, wherein the electromagnetic valve switch is in a closed state; repeating the operation steps (3) - (5) in the first embodiment, removing residual air in the branch pipe of the micro fluidized bed reactor, opening the fluidization carrier gas, opening the electromagnetic valve to pulse siderite sample into the reactor when the carrier gas concentration detected by the on-line process mass spectrum is stable, and monitoring the gas product CO by the process mass spectrum 2 A curve of the generation of CO is shown in fig. 3 (a). As is clear from comparison of the siderite thermal decomposition gas product formation curves measured without elimination of the branch residual air in FIG. 3 (b), it is clear that the reaction tube branch residual air in FIG. 3 (a) is effective to avoid the component N having a molecular weight of 28 in the air 2 Influence on CO content, more accurate gas product CO can be obtained 2 And the relative content of CO, and further calculating the kinetic parameters of the siderite thermal decomposition reaction.
Claims (4)
1. The method for eliminating measurement deviation caused by residual air of a micro fluidized bed reaction analysis instrument is characterized by comprising the following specific processes:
firstly, arranging a path of protective gas on a micro fluidized bed reactor bypass, controlling the protective gas flow by a mass flowmeter, and removing residual air in a branch pipe of the reactor by switching fluidization carrier gas and the protective gas; then quartz sand is used as a fluidization medium to be filled into a micro fluidized bed reactor, the reactor is heated to a preset temperature, and after the preset temperature is reached, fluidization carrier gas is introduced from the bottom of the micro fluidized bed reactor until the concentration of the carrier gas monitored by mass spectrum in the online process is stable and does not change any more, and the fluidization carrier gas is closed at the moment;
weighing a solid sample to be measured, loading the solid sample into a sample injector of a branch pipe of the micro fluidized bed reactor, introducing protective gas into the branch pipe of the micro fluidized bed reactor filled with the sample to be measured, and monitoring the air content change on line through a process mass spectrum;
introducing fluidizing carrier gas from the bottom of the micro fluidized bed reactor again to stabilize the monitored carrier gas concentration until no change occurs, closing the fluidizing carrier gas, then introducing protective gas into the branch pipe of the micro fluidized bed reactor, opening the fluidizing carrier gas again, repeating the process for 2-3 times until the content of air in the branch pipe of the reactor is stable until no change occurs, indicating that residual air in the branch pipe is completely removed, and closing the protective gas;
introducing fluidizing carrier gas, when reaching a stable fluidization state, rapidly pumping the solid sample pulse to be detected into the micro fluidized bed reactor by controlling the electromagnetic valve, and calculating the dynamics of the reaction according to the relation of the relative content of the gas product monitored on line in the rapid process mass spectrum with the change of time.
2. The method for eliminating measurement deviation caused by residual air in a micro fluidized bed reaction analyzer according to claim 1, wherein the micro fluidized bed reactor bypass system is provided with a mass flowmeter inlet connected with gas and an outlet connected with an inlet of a branch pipe of the micro fluidized bed reactor.
3. The method for eliminating measurement deviation caused by residual air in a micro-fluidized bed reaction analyzer according to claim 1, wherein the gas flow rate of the mass flowmeter of the micro-fluidized bed reactor bypass is lower than 100 mL/min.
4. The method for eliminating measurement deviation caused by residual air in a micro-fluidized bed reaction analyzer according to claim 1, wherein the shielding gas introduced by the micro-fluidized bed reactor bypass is the same as the fluidizing carrier gas introduced from the bottom.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103364521A (en) * | 2012-04-05 | 2013-10-23 | 中国科学院过程工程研究所 | Isothermal differential analysis method and isothermal differential analyzer of gas-solid reactions |
| CN105579844A (en) * | 2013-09-25 | 2016-05-11 | 株式会社岛津制作所 | Gas chromatograph-mass spectrometer |
| CN112255257A (en) * | 2020-08-28 | 2021-01-22 | 华电电力科学研究院有限公司 | Micro spouted bed gas-solid reaction kinetic analysis device and analysis method |
| CN112730573A (en) * | 2020-11-26 | 2021-04-30 | 沈阳化工大学 | Method for testing gas-solid reaction kinetics in product gas atmosphere |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9435774B2 (en) * | 2013-05-30 | 2016-09-06 | Shimadzu Corporation | Gas chromatograph apparatus |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103364521A (en) * | 2012-04-05 | 2013-10-23 | 中国科学院过程工程研究所 | Isothermal differential analysis method and isothermal differential analyzer of gas-solid reactions |
| CN105579844A (en) * | 2013-09-25 | 2016-05-11 | 株式会社岛津制作所 | Gas chromatograph-mass spectrometer |
| CN112255257A (en) * | 2020-08-28 | 2021-01-22 | 华电电力科学研究院有限公司 | Micro spouted bed gas-solid reaction kinetic analysis device and analysis method |
| CN112730573A (en) * | 2020-11-26 | 2021-04-30 | 沈阳化工大学 | Method for testing gas-solid reaction kinetics in product gas atmosphere |
Non-Patent Citations (1)
| Title |
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| Acquiring real kinetics of reactions in the inhibitory atmosphere containing product gases using micro fluidized bed;Xuejing Liu 等;《AIChE JOURNAL》;1-11 * |
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