CN102353716A - High-temperature miniature packed bed reactor oscillating balance and measuring method - Google Patents
High-temperature miniature packed bed reactor oscillating balance and measuring method Download PDFInfo
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- CN102353716A CN102353716A CN2011102981770A CN201110298177A CN102353716A CN 102353716 A CN102353716 A CN 102353716A CN 2011102981770 A CN2011102981770 A CN 2011102981770A CN 201110298177 A CN201110298177 A CN 201110298177A CN 102353716 A CN102353716 A CN 102353716A
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Abstract
The invention relates to a high-temperature miniature packed bed reactor oscillating balance and a measuring method. The balance comprises an oscillating tube, a gas heating system, a fluid pulsation driving device, an oscillating sensor and a data processing centre, wherein the oscillating tube and the oscillating sensor are isolated by vacuum transparent ceramic with high light transmittance. When the measurement is carried out, sample gas and sweep gas are heated simultaneously, and the sample gas generates a pulsating flow under the action of the fluid pulsation driving device to stimulate the oscillating tube to oscillate; a signal of the oscillating frequency of the oscillating tube is received by the oscillating sensor, and then data is collected and analyzed to be fed back to the fluid pulsation driving device, so that the working voltage and the working frequency of the fluid pulsation driving device can be adjusted; and the obtained frequency is stored, the quality change is calculated by an analysis programme, and the calculated result is stored and displayed. The high-temperature miniature packed bed reactor oscillating balance provided by the invention has the characteristics of simple structure, small volume, low cost, high working temperature (as high as 1100 DEG C), convenience in installation and debugging, long service life and the like.
Description
Technical field
The present invention relates to a plurality of fields such as the energy, metallurgy, material, specifically, relate to miniature packed bed reactor vibration balance of a kind of high temperature and measuring method.
Background technology
Fields such as the energy, environment, chemical industry, metallurgy, material relate to the researchs of a large amount of relevant diffusions, absorption and reaction kinetics aspect, the requirement mass change and the rate of change thereof of measurement of species exactly in this process.Usually adopt thermogravimetry (TG) to study its change procedure.
Thermogravimetric analyzer (Thermo Gravimetric Analyzer) abbreviates TGA as, is a kind of instrument that utilizes thermogravimetry (TG) detection material temperature and mass change relation.Thermogravimetric analyzer mainly is made up of several sections such as balance, stove, temperature programmed control system, register systems.The ultimate principle of thermogravimetric analyzer (TGA): under temperature programmed control, the quality of measurement of species is with the temperature variation relation of (or time).When measured matter had distillation, vaporizes, decomposites gas or loses water of crystallization in heating process, tested material mass will change.At this moment thermogravimetric curve just is not straight line but descends to some extent.Through analyzing thermogravimetric curve, just can know that measured matter changes when what are spent, and, can calculate and lose how many materials according to weight loss.Yet it receive programming rate slowly, under serious, the high temperature of gaseous diffusion influence mass resolution decline to a great extent, flow greater than 100ml/min produce noise, have dead volume, the long (restriction of defectives such as 10～30s) of response time.
With coal industry is example.The our times various countries attach great importance to for the development and application of clean coal technology, have carried out number of research projects.Because coal is a kind of multiple component and baroque material of containing, the response characteristic that the coal of separate sources is showed in such as pyrolysis, gasification and combustion process has significant difference.Thereby deeply be familiar with the chemical reaction process of coal, carry out relevant reaction kinetics research and be very important.Also can't satisfy the requirement of industrial reaction process development, reactor design and performance prediction at present through theoretical analysis and numerical evaluation, the understanding course of reaction still mainly depends on experimental technique.Because there are unfavorable factors such as tangible flow irregularity and temperature CONCENTRATION DISTRIBUTION difference in industrial reactor inside; Cause very big difficulty to research process; And accurately estimate and the influence of eliminating these factors often is difficult for accomplishing, thereby the experiment that the researcher carries out the coal reaction kinetics is carried out on the lab setup of especial manufacture usually.
Except using thermobalance, also have silk screen reactor and two kinds of methods of drop tube furnace to measure.Silk screen reactor (Wire-Mesh Reactor; WMR) be mainly used in reaction kinetics research under the high heating rate; But it is compared with the industrial reactor actual conditions and has big gap, and is subjected to the requirement of mesh size restrict selected grain diameter bigger, is generally 106～150 μ m.Drop tube furnace (Drop Tube Furnace; DTF) be widely used in the experimental study of pyrolysis, gasification and the combustion process of coal by domestic and international researcher; It is the important experimental chamber device that carries out the research of coal reaction kinetics of generally acknowledging; It is to rely on air-flow entrained solids reactant to get into the combustion characteristics that reactor is studied coal dust, but its temperature of reaction and heating rate are difficult to accurately control and the coal grain is subjected to gas entrainment and the short of reliable method is accurately measured its surface temperature and movement rate.
For overcoming the drawback of gravitational thermal analysis method; Having occurred a kind of technology on the market can satisfy in real time and don't mass measurement instrument --- the TEOM1500(TaperedElementOscillatingMicrobalanceseries1500 of U.S. Rupprecht&Patashnick company that influenced by the gas diffusion restriction) the pulsation mass analyzer; Be characterized in that inertia balance and reaction bed directly are connected to overall structure; The compulsive reaction air-flow all passes through reaction bed; Make reaction at utmost near desirable little reactiveness of no temperature, concentration gradient, directly obtain true and reliable dynamics data.It has high-quality resolution rate under the high temperature, the restriction that do not extended influence,, gas flow little because of the fluid pulsation dead volume are big, add and depress advantages such as apparatus structure is simple.What but this instrument oscillating tube material adopted is quartzy and 300 series stainless steels; Quartzy can not circulate in long term thermal between 1100 ℃ and room temperature because of the influence that is subjected to increased devitrification resistance; And 300 series stainless steel materials are the non high temperature parelinvar; So working temperature high not enough (＜800 ℃) of this instrument; Compare with the operating temperature range (0～1100 ℃) of conventional thermobalance and also to have a certain distance, thereby limited its range of application.
Summary of the invention
To the problems referred to above; The purpose of this invention is to provide a kind of balance that can vibrate at the miniature packed bed reactor of high temperature of temperature following work up to 1100 ℃; Through design again, solve the problem that exists in the prior art to oscillating tube, high temperature insulating technology and natural frequency measuring system.This invention can not only keep the advantage of TEOM1500 pulsation mass analyser; And the range of application field that can realize range of application is extended to thermobalance, thoroughly solved major defect and the not high enough shortcoming of TEOM1500 working temperature that existing thermobalance is extended influence by gas.The present invention is applicable to nearly all application of existing thermobalance.
To achieve these goals, the present invention realizes through following technical scheme:
The miniature packed bed reactor vibration of a kind of high temperature balance; Comprise oscillating tube, gas heating system, fluid pulsation drive unit, vibration transducer and data processing centre (DPC), isolate with the interior high light transmittance ratio transparent pottery that vacuumizes between said oscillating tube and the vibration transducer.The high light transmittance ratio transparent thermal insulation ceramics adopts the vacuum heat-insulation technology to make vibration transducer resistant detector (750 ℃ of maximum operation (service) temperatures) can satisfy the duty of the maximum operating temperature (1100 ℃) of oscillating tube.
Oscillating tube free end of the present invention is the sample packed bed, and the other end is fixed on the gas piping, and is provided with monkey wrench.Free end is designed to ellipse, guarantees under the fluid pulsation exciting, to keep good direction of vibration property.The effect of monkey wrench is the position of fine adjustment oscillating tube.
Oscillating tube of the present invention adopts the permanent elasticity niobium-base alloy of high temperature material to process, and makes oscillating tube still keep its better elastic performance up to 1100 ℃ in temperature.In be coated with silica-base material film (like Si-20%Fe-20%Cr) or gold-plated (Au) film, the balance of can realizing vibrating can have been widened its range of application in the application in the aggressive atmospheres such as sulfur-bearing, nitrogen, chlorine.
Fluid pulsation drive unit of the present invention is piezoelectric ceramics linear electric machine and pot, drives piston motion to cause that sample gas becomes pulsating fluid clocklike in the pipe.Pot changes voltage through adjustable resistance, in measuring process, regulates the operating voltage and the frequency of drive unit.
Vibration transducer of the present invention is full fiber reflection formula vibration measurement sensor.
Be provided with signal regulating device between vibration transducer of the present invention and the data processing centre (DPC).The electric signal that interference system obtains a little less than, signal regulating device converts measured signal to standard signal that collecting device can be discerned through operations such as amplification, filtering.It is to utilize inner circuit (like wave filter, converter, amplifier etc..) to change the signal kind of input and export it.
Data processing centre (DPC) of the present invention comprises data acquisition, data analysis, data feedback and four parts such as data preservation and demonstration.
The present invention also provides a kind of sensing of reflecting type full-optical fiber easily mode that vibration measuring combines with the fluid pulsation exciting technology to come real-time high-precision to measure the natural frequency of miniature packed bed reactor, has overcome existing TEOM1500 and has adopted laser-transmitting formula natural frequency to measure the defective that light modulation is difficult and maintenance is inconvenient that exists.
The miniature packed bed reactor vibration of a kind of high temperature balance measurement method; Sample is placed in the sample packed bed; Sample gas and sweep gas produce pulsating flow under the effect of fluid pulsation drive unit after heating; The vibration of excited oscillation pipe; Its vibration frequency receives signal by the reflection type optical fiber vibration transducer; Then data are gathered and analyzed; To analyze the back data and feed back to the fluid pulsation generation device to regulate its operating voltage and frequency; Frequency to obtaining is preserved; Calculate mass change by routine analyzer, and result of calculation is preserved and shown.
Vibration transducer acknowledge(ment) signal of the present invention is after collection analysis is carried out in conditioning again.
Data acquisition of the present invention realizes through the high-performance data capture card.
Compared with prior art, the advantage that the present invention had is:
(1) these instrument and equipment are brought up to 1100 ℃ with maximum operating temperature from 800 ℃; Its range of application is expanded greatly; The range of application of being expanded comprises: metallurgical (the compound calcification baking vanadium extraction of ore reduction, roasting such as bone coal, pollucite chloridising roasting), energy environment (pyrolysis of the carbon containing energy, burning, gasification, carbonization), material (decomposition, metal material oxidation kinetics), chemical industry (oxidation of chemicals, reduction, decomposition) etc., thus make it can replace the current thermobalance of widely using.
(2) compare with quartz material, among the present invention owing to adopted high temperature resistant parelinvar niobium-base alloy and pottery, make install and fix, regulate more convenient.
(3) with TEOM1500 in Sun-shading type intensity modulation Fibre Optical Sensor launching fiber with receive the optical fiber align difficulty different be, what adopt among the present invention is the reflection type optical fiber vibration transducer, it is convenient to make that system regulates.
(4) accuracy of instrument of the present invention reaches 0.001mg, can satisfy the requirement of a plurality of fields for measuring accuracy fully.
Description of drawings
Accompanying drawing 1 is the structural representation of the miniature packed bed reactor vibration of high temperature balance;
Accompanying drawing 2 is oscillating tube and vibration transducer probe protection structural representation.
The 2 full fiber reflection formula vibration measurement sensor 4 signal regulating devices 5 data acquisitions 6 data analyses 7 data preservations of 1 oscillating tube are fed back in 9 gas heating systems, 10 pistons, 11 fluid pulsation drive units, 12 sweep gas, 13 sample gas, 14 monkey wrenches, the 15 sample packed beds 16 with demonstration 8 data and are vacuumized the high light transmittance ratio transparent pottery
Down in the face of further explain of the present invention.But following instance only is a simple and easy example of the present invention, does not represent or limits rights protection scope of the present invention, and interest field of the present invention is as the criterion with claims.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:
Like Fig. 1, shown in Figure 2; The miniature packed bed reactor vibration of a kind of high temperature balance; Comprise oscillating tube 1, gas heating system 9, fluid pulsation drive unit 11, full fiber reflection formula vibration measurement sensor 2 and data processing centre (DPC); Oscillating tube 1 free end is oval; As sample packed bed 15; The other end is fixed on the gas piping, and is provided with the monkey wrench 14 of fine adjustment oscillating tube position.Oscillating tube 1 adopts the permanent elasticity niobium-base alloy of high temperature material to process, and makes oscillating tube 1 still keep its better elastic performance up to 1100 ℃ in temperature; In be coated with silica-base material film (like Si-20%Fe-20%Cr) gold-plated (Au) film, the balance of can realizing vibrating can be used in aggressive atmospheres such as sulfur-bearing, nitrogen, chlorine.Isolate with the interior high light transmittance ratio transparent pottery 16 that vacuumizes between oscillating tube 1 and the vibration transducer 2, adopt the vacuum heat-insulation technology that the maximum operation (service) temperature (750 ℃) of vibration transducer resistant detector and the maximum operating temperature (1100 ℃) of oscillating tube are complementary.Fluid pulsation drive unit 11 is piezoelectric ceramics linear electric machine and pot, drives piston 10 motions to cause that sample gas becomes pulsating fluid clocklike in the pipe.Be provided with signal regulating device 4 between vibration transducer 2 and the data processing centre (DPC), measured signal is amplified.Data processing centre (DPC) comprises data acquisition 5, data analysis 6, data feedback 8 and four parts such as data preservation and demonstration 7.
Sample gas is the pulsating fluid state under the effect of fluid pulsation drive unit; The vibration of excited oscillation pipe; Measure the natural frequency of oscillating tube by full fiber reflection formula vibration measurement sensor; The oscillation amplitude of oscillating tube is controlled the pulsating flow vibration amplitude by FEEDBACK CONTROL, runs into the gas tube wall to prevent oscillating tube.Owing to adopted permanent elasticity niobium-base alloy of high temperature or high resiliency pottery as the oscillating tube material, so the adjusting of the location of oscillating tube is more convenient.
Measuring method of the present invention is specific as follows: sample is contained in taper oscillating tube free end; Sweep gas 12 reaches the predetermined working temperature of experiment with sample gas 13 after bringing-up section; Sample gas produces the pulsating flow of certain amplitude-frequency under the effect of fluid pulsation drive unit, when its frequency equates with the natural frequency of taper oscillating tube, produce resonance.The frequency of oscillation of taper oscillating tube is by full fiber reflection formula vibration measurement sensor received signal; The signal of telecommunication that interference system obtains a little less than; Behind signal condition by the collection of high-performance data capture card and carry out software processing and analysis; Data after the analysis feed back to the fluid pulsation drive unit to regulate the operating voltage and the frequency of exciting device; Preserve by " Li Sa educates the figure method " judgement resonance point and to the intrinsic frequency that obtains; And calculate mass change by routine analyzer according to intrinsic frequency; Result of calculation is preserved and shown that accuracy of instrument reaches 0.001mg.
Adopt reflecting type full-optical fiber sensor and fluid pulsation exciting technology real-time high-precision to measure the intrinsic frequency of miniature packed bed reactor; Vacuumize the high light transmittance ratio transparent pottery in the utilization and protected reflecting type full-optical fiber sensor resistant detector; The existing TEOM1500 of packed bed reactor oscillating tube breakthrough that is formed by high temperature niobium-base alloy or high resiliency ceramic makes operating temperature be lower than 800 ℃ defective because of adopting quartz or 300 series stainless steels as the oscillating tube material; Make range of application obtain widening greatly, become favorable substitutes with the serious thermobalance that extended influence.
Applicant's statement; The present invention illustrates detailed construction characteristic of the present invention and measuring method through the foregoing description; But the present invention is not limited to above-mentioned detailed construction characteristic and measuring method, does not mean that promptly the present invention must rely on above-mentioned detailed construction characteristic and measuring method could be implemented.The person of ordinary skill in the field should understand, to any improvement of the present invention, to the equivalence replacement of the selected parts of the present invention and the increase of accessory, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the miniature packed bed reactor vibration of high temperature balance; It is characterized in that; Comprise oscillating tube (1), gas heating system (9), fluid pulsation drive unit (11), vibration transducer (2) and data processing centre (DPC), isolate with the interior high light transmittance ratio transparent pottery (16) that vacuumizes between said oscillating tube (1) and the vibration transducer (2).
2. balance as claimed in claim 1 is characterized in that, described oscillating tube (1) free end is sample packed bed (15); The other end is fixed on the gas piping, and is provided with monkey wrench (14).
3. balance as claimed in claim 1 or 2 is characterized in that, described oscillating tube (1) adopts the permanent elasticity niobium-base alloy of high temperature material to process; In be coated with silica-base material film or gold coated films.
4. like the described balance of one of claim 1-3, it is characterized in that described fluid pulsation drive unit (11) is piezoelectric ceramics linear electric machine and pot, drive piston (10) motion to cause that sample gas becomes pulsating fluid clocklike in the pipe.
5. like the described balance of one of claim 1-4, it is characterized in that described vibration transducer (2) is full fiber reflection formula vibration measurement sensor.
6. like the described balance of one of claim 1-5, it is characterized in that, be provided with signal regulating device (4) between described vibration transducer (2) and the data processing centre (DPC).
7. like the described balance of one of claim 1-6, it is characterized in that described data processing centre (DPC) comprises that data acquisition (5), data analysis (6), data feedbacks (8) and data are preserved and demonstration four parts such as (7).
8. the miniature packed bed reactor vibration of high temperature balance measurement method; It is characterized in that; Sample is contained in the sample packed bed (15); Sample gas (13) and sweep gas (12) are heated simultaneously; And sample gas produces pulsating flow under the effect of fluid pulsation drive unit (11); Excited oscillation pipe (1) vibration; Its vibration frequency receives signal by full fiber reflection formula vibration measurement sensor (2); Then data are gathered; Analyze; Feed back to fluid pulsation drive unit (11) to regulate its operating voltage and frequency; Frequency to obtaining is preserved, and calculates mass change by routine analyzer, and result of calculation is preserved and shown.
9. measuring method as claimed in claim 8 is characterized in that, described vibration transducer (2) receives signal after collection analysis is carried out in conditioning again.
10. like claim 8 or 9 described measuring methods, it is characterized in that described data acquisition (5) realizes through the high-performance data capture card.
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| CN 201110298177 CN102353716B (en) | 2011-09-30 | 2011-09-30 | High-temperature miniature packed bed reactor oscillating balance and measuring method |
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| CN 201110298177 CN102353716B (en) | 2011-09-30 | 2011-09-30 | High-temperature miniature packed bed reactor oscillating balance and measuring method |
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| CN102353716B CN102353716B (en) | 2013-03-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012555A (en) * | 2018-10-15 | 2018-12-18 | 武汉亚华电炉有限公司 | A kind of drop tube furnace |
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| US4912962A (en) * | 1986-12-29 | 1990-04-03 | Kyoto Electronics Manufacturing Co., Ltd. | Method of detection of oscillation period for oscillatory densimeter |
| US6156578A (en) * | 1998-06-01 | 2000-12-05 | Advanced Technology Materials, Inc. | Quartz crystal microbalance system for detecting concentration of a selected gas component in a multicomponent gas stream |
| DE102008023056A1 (en) * | 2008-05-09 | 2009-11-12 | Endress + Hauser Flowtec Ag | Coriolis-mass flow rate measuring sensor for use in pipeline for measuring mass flow rate of e.g. gas, has sample exhibiting areas with optical characteristics assigned so that gradient of intensity of light reproduces oscillation of tube |
| CN101738433A (en) * | 2009-11-27 | 2010-06-16 | 西南科技大学 | Device and method for detecting gas concentration by using resonance frequency of gas tank |
| CN102159942A (en) * | 2008-09-19 | 2011-08-17 | 哈里伯顿能源服务公司 | Apparatus and method for detecting fluid characteristic |
-
2011
- 2011-09-30 CN CN 201110298177 patent/CN102353716B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912962A (en) * | 1986-12-29 | 1990-04-03 | Kyoto Electronics Manufacturing Co., Ltd. | Method of detection of oscillation period for oscillatory densimeter |
| US6156578A (en) * | 1998-06-01 | 2000-12-05 | Advanced Technology Materials, Inc. | Quartz crystal microbalance system for detecting concentration of a selected gas component in a multicomponent gas stream |
| DE102008023056A1 (en) * | 2008-05-09 | 2009-11-12 | Endress + Hauser Flowtec Ag | Coriolis-mass flow rate measuring sensor for use in pipeline for measuring mass flow rate of e.g. gas, has sample exhibiting areas with optical characteristics assigned so that gradient of intensity of light reproduces oscillation of tube |
| CN102159942A (en) * | 2008-09-19 | 2011-08-17 | 哈里伯顿能源服务公司 | Apparatus and method for detecting fluid characteristic |
| CN101738433A (en) * | 2009-11-27 | 2010-06-16 | 西南科技大学 | Device and method for detecting gas concentration by using resonance frequency of gas tank |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012555A (en) * | 2018-10-15 | 2018-12-18 | 武汉亚华电炉有限公司 | A kind of drop tube furnace |
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