Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N25/00—Investigating or analyzing materials by the use of thermal means
  • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
  • G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
  • G01N25/4873—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a flowing, e.g. gas sample
  • G01N25/488—Details

Definitions

• the invention belongs to the field of scientific testing methods and instruments, and relates to a gas-solid reaction isothermal micro-differentiation method applied in chemical, chemical, energy, environmental, material, biological and other industrial industries, and a reaction analyzer based on the method, specifically, relating to gas solidification Reaction isothermal differential differentiation analysis method and isothermal differential analyzer. Background technique
• the reactor is the core device for industrialization of chemical reactions, and optimization is a very complicated task. Chemical reaction kinetics analysis and reaction mechanism studies are important basis for reactor optimization. Without accurate measurement and mastery of reaction mechanisms and kinetic laws, it is impossible to create advanced reactors. Therefore, reliable modern reaction kinetics testing and reaction mechanism analytical instruments have a very important position.
• the integral measurement method refers to the measurement of the gas breakthrough (release) curve in a fixed bed or fixed fluidized bed reactor using a large amount of experimental sample.
• the integral kinetic method a reaction kinetic expression is presupposed, The curve is fitted to calculate the kinetic parameters.
• the integral reaction is susceptible to the heat and mass transfer complexity of the reaction itself and the reactor's own conditions.
• the differential reaction test requires only a small amount of sample, and the gas concentration change is small.
• the experimental data is firstly calculated by the differential differentiation method, and the kinetic parameters of the chemical reaction and the reaction mechanism are calculated according to the measured reaction rates at different temperatures. Based on the accuracy and operability of experimental data, the differential method is more suitable for the study of gas-solid reaction kinetics and reaction mechanism.
• TG and DSC can achieve the micro-differentiation of the reaction. It uses a temperature-programmed method to study the reaction rate of the reaction at any temperature, and derives the Arrhenus curve, which can be investigated. Relationship with pressure, gas reactant components, and the like.
• This differential reaction analysis represents a typical thermal analysis method. The process of studying the gas-solid reaction is to place a certain amount of sample in the sample cell, and monitor the quality and morphology of the solid sample in real time during the temperature programming process (visual XRD, EM, etc.).
• thermogravimetry requires only a small amount of sample (differential reactor), and the accurate monitoring of the change in the quality of the reaction process and the accurate control of the heating rate of the heater make it widely used.
• thermogravimetric analyzers cannot test the reaction at any fixed temperature. Reaction characteristics.
• thermogravimetric analysis is difficult to apply to analytical tests with the above-described characteristics but ubiquitous gas-solid reactions. Due to the above-mentioned deficiencies of the temperature-programmed thermogravimetric analyzer, the kinetic parameters calculated from the rate of weight loss are also difficult to describe the intrinsic kinetic characteristics of the chemical reaction control zone.
• the furnace is first heated to the set temperature under the desired gas atmosphere and without the reaction tank, and then quickly moved up quickly, and the reaction material is loaded.
• the reaction cell is incorporated into the heating furnace to accelerate the temperature rise of the reaction cell and initiate a chemical reaction. Since the reaction cell itself does not move, the method can analyze the reaction kinetics by measuring the change in the weight of the material in the reaction cell. Relying on the method of lifting the furnace to achieve rapid temperature rise of the sample is usually easy to cause the fluctuation of the balance during the heating process, which makes the measurement error larger; at the same time, the radiation heating of the furnace wall alone can not achieve the real rapid temperature rise of the sample in the reaction cell (although The thermograviity itself is fast) and, therefore, cannot be a rigorous isothermal kinetic analysis method and instrument.
• Another type of device is a differential reactor that analyzes the kinetic characteristics of the reaction by analyzing changes in the gas product after the reaction.
• Bench-scale fluidized bed reactors eg, Megarities et ⁇ , Energy & Fuels, 1998, Vol. 12, pp. 144-151
• Drop-tube furnaces eg Hayashi et ⁇ , Fuel, 2000, Vol. 79, pp 439-447
• Mesh heaters and Curie-point reactors have long been used to study the rapid thermal decomposition characteristics of fuels (eg Wiktosson and Wanzl, Fuel, 2000, Vol. 79, pp. 701-716).
• the large-size fluidized bed reactor is also used to study the gas-solid reaction kinetics. It can realize and simulate the reaction process in actual engineering. It is easier to achieve the supply of solid materials at a fixed temperature. The heating rate is fast, but these large sizes
• the reactor is a similar reactor to Bench-scale (eg, Megarities et ⁇ , Energy & Fuels, 1998, Vol. 12, pp. 144-151), such as 40 to 100 mm in diameter and 500 to 1000 mm in height, etc. Not a true differential reactor.
• the mixing and diffusion processes of gases present in such reactors must present difficulties and inaccuracies in measuring the reaction kinetics of rapid reactions such as thermal decomposition of biomass.
• the object of the present invention is to provide an analytical method for realizing isothermal micro-differentiation reaction, which adopts a micro-fluidized bed as a core of a reactor, and integrates the instantaneous pulse injection of the fine particle reactant sample and the on-line rapid monitoring of the generated gas.
• an isothermal differential gas-solid reaction analyzer which can be widely used under various conditions is provided.
• the gas-solid reaction isothermal micro-differentiation analysis method of the invention provides a micro-particle reactant to a fluidized bed through a transient pulse sampling system, and combines the transient pulse gas transport injection of the fine particle reactant with the gas product composition concentration and On-line monitoring of flow, rapid heating of reaction materials and isothermal micro-differentiation under isothermal conditions,
• the transient pulse sampling system comprises: a gas solid sample injection tube 15, a pulse solenoid valve 14 and a gas cylinder A34; the injection gas A in the gas cylinder A34 is controlled by a pulse solenoid valve 14 to inject a transient pulse into the solid Sample injection tube 15 for transient pulse injection.
• the transient pulse sampling system further includes: a gas check valve 11, a gas quantitative pipe 12, a gas mass flow meter A37; the injection gas A in the gas cylinder A34 is filled with the gas quantitative pipe 12 through the gas mass flow meter A37 and the check valve 11, and the transient pulse is injected into the solid sample injection pipe 15 by the pulse electromagnetic valve 14 to realize the transient state. Pulse injection.
• the compressed gas is injected into the gas metering tube 12 through the gas check valve 11 and stored in the gas metering tube 12, and by controlling the opening degree (range) of the gas mass meter A37, the gas in the gas metering tube 12 is quickly passed.
• the flow meter brings the material into the reactor for reaction to achieve transient transport of the material.
• the gas-solid reaction isothermal differential differentiation analysis method according to the present invention, wherein the method specifically comprises the following steps:
• Gas B in gas cylinder B35, gas C in gas cylinder C36 is passed through the valve of gas mass flow meter B10 and gas mass flow meter C33 into the two-stage micro fluidized bed 7, and the gas flow rate is set at the reaction temperature.
• the apparent gas flow rate in the two-stage microfluidizer bed 7 is greater than the initial fluidization velocity of the fluidized particles 5 and less than the take-up speed;
• the sampling program on the single chip microcomputer 21 controls the pulse solenoid valve 14, adjusts the opening and closing time of the pulse solenoid valve 14, and advances in the gas cylinder A34.
• the sample gas A is injected into the solid sample injection tube 15 through the gas mass flow meter A37 and the check valve 11 and is filled with the gas quantitative tube 12, so that the fine particle reactant 19 is injected into the double-stage micro fluidized bed 7 for instantaneous temperature rise.
• the temperature and pressure of the two-stage microfluidizer bed 7 and the concentration of the key product of the reaction change with time through the temperature controller 3, the pressure sensor 9, the fast process mass spectrometer 18, the pressure gauge 20, the control chip 13, and the computer 21 monitoring;
• the fluidized particles 5 have a particle diameter of 30 to 1000 ⁇ and a static aspect ratio of less than 3.
• the gas-solid reaction isothermal differential differentiation analysis method according to the present invention, wherein the method specifically comprises the following steps:
• the biomass material is added to the lower layer of the micro fluidized bed 7 through a transient pulse sampling system for reaction, and the gaseous tar produced by the biomass material in the lower layer is subjected to a cracking reaction through the upper layer;
• the tar is injected into the bottom of the micro-fluidized bed 7 through a liquid atomization injector 29 in a trace gaseous state, and the cleavage reaction is carried out through the lower layer and the upper layer of the micro-fluidized bed 7 with the gas;
• the fine coal particles are passed through a transient pulse sampling system into a single-stage micro-fluidized bed for rapid pyrolysis reaction. After the pyrolysis semi-coke particles pass through the cyclone separator 30, the gaseous products are detected by rapid process mass spectrometry 18; 2) After the pyrolysis semi-coke particles pass through the cyclone separator 30, the solid product enters the lower layer of the two-stage micro-fluidized bed 7 for combustion reaction, and the gas generated by the combustion reaction is detected by the gas purification and detection system.
• the pulse solenoid valve 14 is controlled to open and close at 0.01-1 s.
• the pressure of the injection gas A is controlled to be 0.1-0.5 MPa.
• the isothermal micro-differentiation reaction analyzer of the present invention comprises a micro fluidized bed 7, a temperature and pressure control system, a gas purification and detection system, and a data acquisition and analysis system; the gas-solid reaction analyzer further includes an instantaneous State pulse injection system;
• the transient pulse sampling system comprises: a gas solid sample injection tube 15, a pulse solenoid valve 14 and a gas cylinder A34; the injection gas A in the gas cylinder A34 is controlled by a pulse solenoid valve 14 to inject a transient pulse into the solid Sample injection tube 15 for transient pulse injection.
• the isothermal micro-differentiation reaction analyzer wherein the micro-fluidized bed 7 is a two-stage micro-fluidized bed; the gas distribution plate 24 made of a quartz sintered plate, a ceramic foam plate or a metal sieve plate is divided into Upper and lower two-layer structure, diameter 5-50 mm, upper layer height 20-100 mm, lower layer height 20-100 mm, upper layer filling height 10-50 mm, casing with externally threaded armored thermocouples on both sides of the lower layer 23 and the injection tube cannula 25.
• the gas distribution plate 24 made of a quartz sintered plate, a ceramic foam plate or a metal sieve plate is divided into Upper and lower two-layer structure, diameter 5-50 mm, upper layer height 20-100 mm, lower layer height 20-100 mm, upper layer filling height 10-50 mm, casing with externally threaded armored thermocouples on both sides of the lower layer 23 and the injection tube cannula 25.
• the isothermal micro-differentiation reaction analyzer according to the present invention, wherein the temperature and pressure control system is composed of a micro electric furnace 6, a temperature sensor 4, a temperature controller 3, a pressure sensor 9, a pressure gauge 20, and a back pressure valve 1.
• the gas purification and detection system consists of a microfilter 2, a fast process mass spectrometer 18, a gas detector 17, and a flow sensor 16.
• the data acquisition and analysis system is composed of a control chip 13, a single chip microcomputer 21, a data processing and a dynamic parameter calculation module.
• the micro fluidized bed containing the fluidized particles 5 is located inside the micro electric furnace 6, and the microfluidized bed is provided with belts on both sides.
• the externally threaded armature thermocouple sleeve 23 and the sample tube sleeve 25, the temperature sensor 4 is inserted into the microreactor 7 through the sleeve 23 of the armored thermocouple, and connected to the micro electric furnace 6 through the temperature controller 3;
• the injection tube cannula 25 is connected to the material outlet tube of the solid sample injection tube 15.
• the gas outlet tube at the upper portion of the microreactor 7 is sequentially connected to the microfilter 2, the fast process mass spectrometer 18, the back pressure valve 1 and the gas detector 17, the pressure gauge 20 is located at the outlet of the microreactor 7, and the back pressure valve 1 is located at the micro At the exit of the filter 2.
• the input end of the pressure sensor 9 is connected to the lower gas inlet of the micro fluidized bed 7, and the output end of the pressure sensor 9 is connected to the outlet of the microreactor 7; the inlets of the gas mass flow meter B10 and the gas mass flow meter C33 are respectively connected with the gas cylinder B35, The pressure reducing valve of the gas cylinder C36 is connected, and after the outlet is passed through the mixer 8, the micro fluidized bed 7 is directly connected.
• the micro electric furnace 6, the pressure sensor 9, the pulse solenoid valve 14, the flow sensor 16, the gas detector 17, the fast process mass spectrometer 18, the gas mass flow meter A37, the gas mass flow meter B10, and the gas mass flow meter C33 all pass the control chip. 13 is connected to the single chip microcomputer 21.
• All data such as flow rate, pressure, temperature, and concentration of key products in the reactor outlet gas are collected by the data control chip 13 and then sent to the single-chip microcomputer 21 for analysis and processing.
• the isothermal micro-differentiation reaction analyzer according to the present invention, wherein the micro-fluidized bed 7 is a two-stage micro-fluidized bed, the lower side wall is provided with a sample tube sleeve connected to the sample tube, and the lower end is filled with a liquid. Atomizer injector 29.
• the isothermal micro-differentiation reaction analyzer according to the present invention, wherein the micro-fluidized bed 7 is a two-stage micro-fluidized bed, and the lower side wall is connected to another single-stage micro-fluidized bed through a cyclone separator 30,
• the side wall of the single-stage micro fluidized bed is provided with a sample tube sleeve connected to the sample tube, and the upper portion of the cyclone separator 30 has a gas outlet.
• the isothermal micro-differentiation reaction analyzer according to the present invention, wherein the micro-fluidized bed 7 is a single-stage micro-fluidized bed with a built-in guide tube, and the side wall is higher than the micro-electric furnace 6 with a sample tube sleeve connection
• a solid collector 31 is connected above the side wall gas distribution plate, and a liquid feed pipe is connected to the lower part, and one end of the liquid feed pipe extends into the gas distribution plate in the double-stage micro fluidized bed 7, and one end is placed in the pre-preheating Inside the hot electric furnace 32.
• thermocouple a temperature sensor 4 which is fixed to the sleeve 23 of the armored thermocouple by a PTFE ferrule nut 22;
• the sample tube 15 is secured to the sample tube cannula 25 by a PTFE cap nut #38.
• the gas purification and detection system comprises a microfilter 2 and a fast process mass spectrometer 18;
• the microfilter 2 is made of glass, polytetrafluoroethylene or stainless steel.
• the adsorption filter packing 26 and the glass filter fiber sleeve 27 are disposed, and the adsorption filter packing 26 is located at the bottom of the glass filter fiber sleeve 27 with a gap therebetween; the rapid process mass spectrum 18 has a capillary tube 28,
• the ferrule connection is secured within the glass filter fiber sleeve 27.
• the working principle and data processing method of the isothermal differential differentiation analyzer are as follows: When the temperature is stable, and the fluidized particles 5 in the micro fluidized bed 7 are in a state of stable fluidization or vigorous turbulence, the fine particle reactant 19 is injected into the micro fluidized bed 7 at a rate of 15-30 m/s. In the fluidized particles 5, the reaction has good heat transfer and mass transfer, the solid reactant is instantaneously heated to a set reaction temperature to start the reaction, and a micro shallow fluidized bed reaction is used, and the gas product is in the reactor. Approximate flat push flow. Therefore, the reaction is considered to proceed under isothermal differential conditions.
• the time at which the gas product obtained by the reaction exits the microfluidizer bed 7 and passes through the microfilter 2 to the gas detector 17 is referred to as the system reaction delay, which can be determined in advance by a gas tracer method. Therefore, the timing at which the pulse solenoid valve 14 of the transient pulse injection system is turned on and the microparticle fluid reactant is supplied to the micro fluidized bed 7 can be determined as the start time of the reaction, and the time at which the reaction ends should be the time when the single chip microcomputer 21 stops sampling. Subtract the system's reaction delay time. Of course, if the system's response delay time is small enough, it can be ignored in the data processing process.
• the amount of the fine particle reactant added on the line is extremely small, the amount of gas flowing out of the micro fluidized bed 7 is similar to the total gas amount passing through the gas mass flow meter and the gas quantitative pipe 12, and may also be based on the gas mass flow rate of the gas outlet.
• the meter shows the change in flow rate and the integration of time. In this way, the reaction rate at the reaction temperature and pressure can be easily determined according to the concentration change of the key product of the reaction, and the reaction kinetic parameters such as the activation energy of the reaction are further calculated according to the Arrhenius equation; or according to the gas concentration and the release sequence.
• the reaction mechanism is estimated and the amount of gas adsorption is calculated.
• the innovative technical idea of the method is: using a fluidized bed to enhance the heat transfer and mass transfer between the reactant sample, the fluidized medium (bed material) and the gas, to minimize the inhibition of the reaction by the external diffusion and thereby cause
• the reaction temperature is not uniform;
• the micro-fluidized bed reactor combines the transient gas pulse injection to transport the micro-fine particle sample into the reactor to realize the micro-differentiation of the gas-solid reaction, and at the same time, the gas is close to the flat flow in the reactor.
• the particles are similar to the full mixed flow; the gas-solid reaction of different kinds of solid samples, bed materials, and different characteristics, such as particle vapor deposition, cascade reaction in situ classification, liquid phase reactants, is realized by using a microfluidic bed of various structures.
• the main features of the isothermal differentially differentiated reaction analyzer of the present invention are distinguished from a reaction bed similar to a fixed bed in TGA, or a Bench-scale reactor (Megarities et ⁇ , Energy & Fuels, 1998, Vol. 12, pp. 144- 151) and larger fluidized bed reactors used in the Drop-tube furnace (Hayashi et al., Fuel, 2000, Vol. 79, pp. 439-447), using two shallow microfluidics
• the bed serves as a reaction cell.
• the technical effects that can be achieved are: (1) using a fluidized bed as a reactor to enhance the heat transfer and mass transfer of the reaction; (2) using a microreactor and a micro-fine solid reactant transient reverse jet to achieve any reaction temperature Gas-solid reaction analysis; (3) The characteristics of gas-solid flow in the micro-fluidized bed to realize the solid mixed flow and the gas flat flow, effectively ensuring the isothermal differential characteristics of the gas-solid reaction, so that the reaction kinetic parameters at any reaction temperature can be determined. Made possible; (4) Fast online monitoring tools such as mass spectrometry, infrared gas analysis Instruments, electrochemical sensors, etc. enable rapid detection of gas composition and concentration to ensure data accuracy.
• FIG. 1 is a schematic diagram of an isothermal differential differentiation analysis method for a gas-solid reaction of the present invention
• FIG. 2 is a schematic view of an isothermal differential differentiation reaction analyzer of the present invention
• FIG. 3 is a schematic diagram of a micro fluidized bed of an isothermal micro-differentiation reaction analyzer of the present invention (two-stage gas-solid reaction fluidized bed);
• FIG. 4 is a schematic view showing the structure of a microfilter of an isothermal differential differentiation reaction analyzer of the present invention.
• Fig. 5 is a schematic view of a micro fluidized bed of an isothermal micro-differentiation reaction analyzer of the present invention (biomass tar in-situ pyrolysis fluidized bed).
• Fig. 6 is a schematic view of a micro fluidized bed of an isothermal micro-differentiation reaction analyzer of the present invention (coal pyrolysis combustion decoupling reaction fluidized bed).
• Fig. 7 is a schematic view of a microfluidized bed (with a draft tube and a solid sampler) of the isothermal differential differentiation reaction analyzer of the present invention.
• Fig. 8 is a schematic diagram showing the design of a solid collector of an isothermal differential differentiation reaction analyzer of the present invention.
• Micro Fluidized Bed Reactor ⁇ Transient Pulse Injection System III, Detection System VI, Integrated Software and Hardware 1. Back Pressure Valve 2. Micro Filter 3. Temperature Controller 4. Temperature Sensor
• Gas detector 18 fast process mass spectrometer 19, fine particle reactant 20, pressure gauge 21, single chip microcomputer 22, PTFE sleeve nut 23, sleeve 24 for armored thermocouple, gas distribution plate 25, injection Tube sleeve 26, adsorbent filter packing 27, filter glass fiber sleeve 28, capillary 29, liquid atomizer injector 30, micro cyclone 31, solids collector 32, preheating furnace 33, gas mass flow meter C 34 , Gas cylinder A 35, gas cylinder B 36, gas cylinder C 37, gas mass flow meter A 38, PTFE sleeve nut II 39, liquid nitrogen cold well 40, vacuum pump embodiment
• the principle of the gas-solid reaction isothermal micro-differentiation method of the present invention is shown in Fig.
• the fluidizing gas velocity is selected between the initial fluidization velocity of the bed pellet and the entrainment velocity of the pellet. (0.1-lm/s).
• the transient pulse sampling system uses a pulse method to rapidly inject a small amount of fine particles into the lower layer of the micro fluidized bed through a high-speed carrying airflow to achieve a gas flow in the microfluidized bed, and between the sample and the fluidized particles.
• the mixing is similar to the gas-solid flow state of the full mixed flow, achieving rapid heating of the reaction mass and isothermalization of the reaction, and because of the use of the micro fluidized bed reactor, the reaction micro-differentiation under the conditions of minimizing diffusion inhibition and isothermal conditions is achieved.
• the generated gas of the isothermal differential reaction is quickly evaded by the detection system m to detect the concentration, composition, and flow rate, thereby ensuring online capture of the reaction information.
• the method of achieving isothermal microdifferentiation of the gas-solid reaction is centrally controlled and operated by a matched integrated hardware and software VI.
• the gas-solid reaction isothermal differential differentiation analysis method of the present invention supplies a fine particle reactant to a fluidized bed through a transient pulse sampling system, and combines the transient pulse gas transport injection of the fine particle reactant with the concentration and flow rate of the gas product composition.
• the transient pulse sampling system includes: gas solid sample injection tube 15, pulse solenoid valve 14 and gas cylinder A34, gas sheet To the valve 11, the gas quantitative tube 12, the gas mass flow meter A37; the injection gas A in the gas cylinder A34 is controlled by the pulse solenoid valve 14 to inject a transient pulse into the solid sample injection tube 15 to effect transient pulse injection.
• the injection gas A in the gas cylinder A34 is filled with the gas quantitative tube 12 through the gas mass flow meter A37 and the check valve 11, and the transient pulse is injected into the solid sample injection tube 15 by the pulse electromagnetic valve 14 to realize the transient pulse advancement. kind.
• the gas-solid reaction isothermal differential differentiation analysis method of the present invention comprises the following steps:
• the two-stage microfluidizer bed 7 containing the fluidized particles 5 is fixed in the temperature equalization zone of the micro electric furnace 6, and the fine particle reactant 19 is placed in the solid sample injection pipe 15, wherein the fluidized particles 5
• the particle diameter is 30-1000 ⁇ , and the static height-to-diameter ratio is less than 3
• the sampling program on the single chip microcomputer 21 controls the pulse solenoid valve 14, adjusts the opening and closing time of the pulse solenoid valve 14, and the opening and closing time of the pulse solenoid valve 14
• Sample tube 15 The fine particle reactant 19 is injected into the two-stage micro fluidized bed 7 to instantaneously raise the temperature to initiate the reaction.
• the temperature and pressure of the two-stage micro fluidized bed 7 and the concentration of the key product of the reaction change with time through the temperature controller 3, pressure The sensor 9, the fast process mass spectrometer 18, the pressure gauge 20, the control chip 13 and the computer 21 monitor; 4) When the concentration of the reaction key product drops below 1.0%, the sampling is stopped, and the single chip 21 analyzes the data and outputs the measurement result.
• the isothermal micro-differentiation reaction analyzer of the present invention comprises a micro fluidized bed 7, temperature and pressure control System, gas purification and detection system and data acquisition and analysis system; the gas-solid reaction analyzer further comprises a transient pulse injection system; the transient pulse injection system comprises: a gas solid sample injection tube 15. Pulse solenoid valve 14 and gas cylinder A34; Sample gas A in gas cylinder A34 is controlled by pulse solenoid valve 14 to inject a transient pulse into solid sample injection tube 15 for transient pulse injection.
• the micro fluidized bed 7 is a two-stage micro fluidized bed; the gas distribution plate 24 made of quartz sintered plate, ceramic ceramic plate or metal sieve plate is divided into two upper and lower layers, the diameter is 5-50 mm, and the upper layer height 20-100 mm, lower layer height 20-100 mm, upper layer filling height 10-50 mm, both sides of the lower layer are provided with an externally threaded armored thermocouple sleeve 23 and a sample tube sleeve 25.
• the temperature and pressure control system consists of a micro electric furnace 6, a temperature sensor 4, a temperature controller 3, a pressure sensor 9, a pressure gauge 20, and a back pressure valve 1.
• the gas purification and detection system is composed of a microfilter 2, a fast process mass spectrometer 18, a gas detector 17, a flow sensor 16, and the microfilter 2 is made of glass, polytetrafluoroethylene or stainless steel, including an adsorption filter filler 26 And a glass filter fiber sleeve 27, the adsorbent filter packing 26 is located at the bottom of the glass filter fiber sleeve 27 with a gap therebetween; the fast process mass spectrum 18 has a capillary tube 28, which is fixed by a ferrule connection The glass filter fiber sleeve 27 is inside.
• the data acquisition and analysis system is composed of a control chip 13, a single chip microcomputer 21, a data processing and a dynamic parameter calculation module.
• the microfluidizer bed 7 containing the fluidized particles 5 is located inside the micro electric furnace 6, and the outer casing of the microfluidizer bed 7 is provided with an externally threaded armored thermocouple sleeve 23 and a sample tube sleeve 25, a temperature sensor 4
• the microreactor 7 is inserted through the sleeve 23 of the armored thermocouple, and is connected to the micro electric furnace 6 through the temperature controller 3; the sample tube sleeve 25 is connected to the material outlet tube of the solid sample injection tube 15.
• the temperature sensor 4 is fixed to the sleeve 23 of the armored thermocouple by a PTFE sleeve nut 22.
• the solid sample injection tube 15 is secured to the sample tube cannula 25 by a PTFE cap nut #38.
• the gas outlet tube at the upper portion of the microreactor 7 is sequentially connected to the microfilter 2, the fast process mass spectrometer 18, the back pressure valve 1 and the gas detector 17, the pressure gauge 20 is located at the outlet of the microreactor 7, and the back pressure valve 1 is located at the micro At the exit of the filter 2.
• the input of the pressure sensor 9 is connected to the lower gas inlet of the microfluidizer bed 7, and the output of the pressure sensor 9 is connected to the outlet of the microreactor 7.
• the inlets of the gas mass flow meter B10 and the gas mass flow meter C33 are respectively connected to the pressure reducing valve of the gas cylinder B35 and the gas cylinder C36, and the outlet is directly connected to the micro fluidized bed 7 through the mixer 8.
• the micro electric furnace 6, the pressure sensor 9, the pulse solenoid valve 14, the flow sensor 16, the gas detector 17, the fast process mass spectrometer 18, the gas mass flow meter A37, the gas mass flow meter B10, and the gas mass flow meter C33 all pass the control chip. 13 is connected to the single chip microcomputer 21. All data such as flow rate, pressure, temperature, and concentration of key products in the reactor outlet gas are collected by the data control chip 13 and then input into the single chip microcomputer 21 for analysis and processing. Specific application and reactor design examples
• the micro fluidized bed 7 is a two-stage micro fluidized bed, the lower side wall is provided with a sample tube sleeve connected to the sample tube, and the lower end inlet is provided with a liquid atomization sampler 29, Online injection reaction analysis of liquids can be achieved.
• the pyrolysis reaction of biomass tar in a two-stage shallow fluidized bed can be carried out in two ways.
• the biomass material is fed into the lower layer of the microfluidized bed 7 through a transient pulse sampling system for reaction, biomass material.
• the tar produced in situ (the lower layer of the micro-fluidized bed) undergoes a cracking reaction through the fluidized particles in the fluidized bed or other bed materials to achieve the cleavage reaction test of the tar.
• the tar can also be injected into the bottom of the micro-fluidized bed 7 through the liquid atomizing injector 29 in a trace gaseous state, and reacts as the fluidizing gas passes through the lower layer of the micro-fluidized bed and the fluidized particles or catalyst layer of the upper layer.
• the cleavage reaction of the tar in the micro fluidized bed is achieved.
• the gas is cleaned and detected by a gas purification and detection system, and the heavy components are analyzed by infrared gas to qualitatively and quantitatively analyze the functional groups. Investigate the in situ cracking mechanism and kinetics of biomass tar.
• the reaction was carried out in two microfluidized beds.
• the micro fluidized bed 7 is a two-stage micro fluidized bed, and the lower side wall is connected to another single-stage micro fluidized bed through a cyclone separator 30, and the side wall of the single-stage micro fluidized bed is provided with
• the sample tube sleeve is connected to the sample tube, and the cyclone separator 30 has a gas outlet at the upper portion thereof.
• the fine coal particles enter a single-stage micro-fluidized bed through a transient pulse feeding system for rapid pyrolysis reaction, and the pyrolysis residence time of the fine coal particles in the fluidized bed is adjusted by adjusting the gas flow rate, and the pyrolysis semi-coke particles pass through.
• the gas product is detected by a gas purification and detection system to analyze the characteristics and kinetics of the rapid pyrolysis reaction; after the pyrolysis semi-coke passes through the cyclone separator 30, the solid product enters the lower layer of the dual-stage microfluidizer bed 7.
• the combustion (gasification) reaction is carried out, and the gas generated by the semi-coke combustion (gasification) reaction is detected by a gas purification and detection system to study the combustion (gasification) reaction characteristics and kinetics of the hot semi-coke.
• the single-stage microfluidized bed pyrolysis reaction and the combustion (gasification) reaction in the two-stage microfluidizer 7 control the flow rate by external gas regulation.
• micro-fluidized bed reactor with a built-in draft tube was developed.
• the micro-fluidized bed 7 is a single-stage micro-fluidized bed with a built-in guide tube, and the side wall is higher than the micro-electric furnace 6 with a sample tube sleeve connected to the sample tube, and a solid material is connected above the side wall gas distribution plate.
• the collector 31 is connected with a liquid feed pipe at the lower portion, and one end of the liquid feed pipe extends above the gas distribution plate in the two-stage micro fluidized bed 7, and one end is placed in the preheating electric furnace 32.
• the fine particle reactant is introduced into the inner tube of the flow guiding structure of the single-stage micro fluidized bed 7 through a transient pulse supply system, and the organometallic compound solution is flowed from the single-stage microflow.
• the liquid feed pipe at the lower end of the chemical bed 7 is injected, and after being heated and heated at a high temperature by the preheating electric furnace 32, it enters the inner tube of the flow guiding structure, and is deposited as a metal oxide on the surface of the particle and reacts with the fine particle reactant.
• the reaction is completed.
• the gas products produced are directly removed upwards and tested by a gas purification and detection system to study the vapor deposition reaction mechanism and reaction kinetics.
• the fine particle reactant reacts with the organometallic compound in the inner tube of the flow guiding structure, and is stabilized by falling into the outer tube of the fluidized bed flow guiding structure due to gravity.
• the flow guiding structure of the reactor effectively isolates the heating zone (outer pipe) from the reaction zone (inner pipe), thereby avoiding the occurrence of vapor deposition reaction on the heating wall.
• the dense dense bed position of the particle is provided with a solid collector 31, and the particles in the reactor can be sampled and analyzed at any time.
• the design principle of the solid collector 31 is as shown in FIG. 8.
• the solid sample enters the cooling bottle of the liquid nitrogen cold well 39, and the vacuum degree of the cooling bottle is adjusted by controlling the opening degree of the vacuum pump 40 and the valve, and simultaneously controlled.
• a valve connected to the microfluidizer bed 7 controls the output of the particles to achieve quantitative collection of solid samples. After the collection, the samples were characterized, and the reaction mechanism and kinetics were studied by online analysis of the gas generated by the chemical deposition process.

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• 2012
  • 2012-04-06 WO PCT/CN2012/073570 patent/WO2013149395A1/fr not_active Ceased

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