CN102706812A - Measurement and control method of supercritical water reaction kettle - Google Patents
Measurement and control method of supercritical water reaction kettle Download PDFInfo
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- CN102706812A CN102706812A CN2012101770457A CN201210177045A CN102706812A CN 102706812 A CN102706812 A CN 102706812A CN 2012101770457 A CN2012101770457 A CN 2012101770457A CN 201210177045 A CN201210177045 A CN 201210177045A CN 102706812 A CN102706812 A CN 102706812A
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Abstract
The invention relates to a measurement and control method of a supercritical water reaction kettle. The measurement and control method is combined with optical fiber spectral online analysis and CCD (charge coupled device) array spectrophotometric testing technologies to perform real-time online monitoring of the supercritical water reaction kettle; when the supercritical water reaction kettle runs, a light source is used for transmitting light with wavelength in the wavelength range of 200-1000nm, the light is transmitted into a reaction kettle body through a high temperature-resistant hologram transmission mechanical, an optical fiber is taken as a signal coupling device for coupling the measured light into a spectrometer in the optical fiber, a CCD array spectrophotometer is used for matching with the optical fiber to get real-time data which is related to an experiment, then a signal converter is used for transmitting the data to an external computer for performing software and result analysis, and a temperature and pressure probe is used for getting the data and entering into the software and result analysis through signal conversion. The measurement and control method disclosed by the invention can be used for researching dynamics and thermodynamics of hydrothermal transformation, hydrothermal oxidation and hydrothermal catalysis of compounds, determine a temperature-effect curve and greatly promote the analysis of a transformation mechanism of the compounds and the optimization of engineering parameters.
Description
Technical field
The present invention relates to the on-line monitoring analytical technology in a kind of environmental protection field, especially relate to a kind of investigating method of supercritical water reaction still.
Background technology
Hypercritical hydrothermal reaction is to be solvent with water, the chemical reaction that under the condition of HTHP, carries out.Advantages such as it is fast that supercritical water has reaction rate, and the process closure is good, and organic solubleness is high, and viscosity coefficient is little, and adaptability is strong are the most promising Green Chemical Technology of generally acknowledging, are one of focuses of current scientific research.This seminar has developed a kind of supercritical water oxidation device of stablizing slagging-off, and the supercritical reaction still has a cover grain slag tripping device, and the slag dirt is directly discharged from the bottom through precipitate and separate, and the WS can smooth and easyly flow out from the top of tripping device.The related patent U.S. Patent No. of application comprises the continuous feed device (ZL200920314622.6) of the high solids content fluid of high pressure reactor. supercritical water oxidation device (ZL200920315890.x). and the straight tube dividing wall type heat exchanger; Realize HTHP hydrothermal treatment consists combination type reactor and disposal route thereof; Handle the high temperature and high pressure flow hydro-thermal device of high solids content fluid etc.
Although yet hypercritical hydrothermal reaction has many advantages, there are a lot of difficulties in its practical application, mainly be for the understanding of supercritical water character and the insufficient recognition of reactant change of properties in supercritical water.Supercritical water reaction is many to be accomplished and the agitated reactor residence time much larger than its reaction time in several seconds or tens seconds; Research major part in the past all adopts through cooled data analysis or through the method that the data under the subcritical state are calculated the mechanism mechanism of its water chemistry reaction is explored; And this with have bigger error in supercritical water real time reaction result; Organism is under different temperatures, because there is certain difference in its molecular structure etc., so the organism collection of illustrative plates also possibly there are differences.And current under higher temperature (in subcritical and overcritical), organism collection of illustrative plates information material lacks very much, measures at normal temperatures mostly.For a certain compound, the collection of illustrative plates Changing Pattern under---subcritical---supercriticality that it is from normal temperature also is difficult to obtain.And the compound reaction kinetics mechanism under the supercriticality; The online detection of thermodynamic parameter is the prerequisite that the mechanism mechanism of supercritical water reaction is explored; But at present also there is not good methods to SCWO character and to the research that influences mechanism of catalyst surface reactivity; Especially the instrument that lacks on-line analysis; Therefore the present invention has developed a kind of supercritical reaction station that works online, and the Millisecond Changing Pattern with data such as the DO in the real-time monitoring supercritical water reaction process, pH, temperature, pressure, conductivity, spectrum will have huge facilitation to the research of hydro-thermal scientific basic.
Summary of the invention
The object of the invention is exactly not have under fine means and the basic blank situation of relevant online analytical instrument to the present mechanism research that influences to supercritical water character and catalyst surface reactivity etc.; Invented a kind of investigating method of supercritical water reaction still; Its core comprises the agitated reactor observation and control technology, and full spectrum on line monitoring technology comprises fiber spectrum on-line analysis and ccd array spectrophotometer technology specifically; The workstation general structure comprises autoclave; High-pressure pump, condenser, the optical fiber of counterbalance valve and the transmission xenon source that in attaching body, inserts and transmit the ccd array spectrophotometer of spectral signal through optical fiber; Also can add and comprise scattering, signal detectors such as refraction.
The object of the invention can be realized through following technical scheme:
A kind of investigating method of supercritical water reaction still; This method combines fiber spectrum on-line analysis and ccd array spectrophotometric measuring technology that the supercritical water reaction still is carried out real-time on-line monitoring; Specifically may further comprise the steps: the supercritical water reaction still is when operation; Light by light emitted wavelength coverage 200-1000nm wavelength imports in the reaction kettle body through the holographic transmission mechanism of resistant to elevated temperatures optical fiber; Optical fiber is as signal coupler spare; With the tested spectrometer that couples light in the optical fiber, use ccd array spectrophotometer and optical fiber to be used to obtain to be transferred to external computer through signal converter after the relevant real time data of experiment and to carry out software and interpretation of result, the temperature, pressure probe obtains data and passes through conversion of signals entering software and interpretation of result.
The reaction volume of described supercritical water reaction still is 0.5～2L, and maximum operation (service) temperature is 400～500 ℃, and maximum working pressure (MOP) is 30.0～40.0Mpa, and the magnetic stirring apparatus maximum speed that agitated reactor uses is 700～800r/min.
Described light source is an xenon source, and single beam has reference beam, holographic grating, and wavelength accuracy 2mm can obtain the all-wave long data of 200-1000nm.
The holographic transmission mechanism of described optical fiber adopts highly sensitive fiber spectrometer to carry out detected transmission, is provided with the spectrophotometer that detects light intensity with fiber optic transmission in the quartz glass tunnel of fiber spectrometer front end.
Described spectrophotometer comprises the entrance slit of source imaging, concave grating and detector.
Described ccd array spectrophotometric is counted linear CCD array format 2048 pixel CCD.
Described temperature, pressure probe is for sensor-type probe, through data collecting card collecting temperature pressure information.
Compared with prior art, the present invention will can be used for the compound hydrothermal conversion, hydrothermal oxidization, and the dynamics of hydro-thermal catalysis and thermodynamic study can be measured the temperature effect curve, can promote the analysis and the through engineering approaches parameter optimization of compound transformation mechanism greatly.The present invention can monitor and write down parameters such as temperature, pressure and time in real time through the digital monitoring interface, removes the potentiality in this experiment that can be generalized to multiple two-phase flow HTHP in addition, in the alcoholysis experiment like the preparation biodiesel.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment
A kind of supercritical water reaction still observation and control technology; Its technological process is as shown in Figure 1; Its technical work station basic structure comprises volume pump 1, agitated reactor 2, condenser 3, counterbalance valve 4, light source 5, optical fiber 6, ccd array detecting device 7, temperature, pressure probe 8 and output result 9.
The volume pump 1 that uses is the high-pressure plunger volume pump, and flow adjustment range is 0-2L/h, and the working pressure maximum can reach 50MP.The reaction volume of agitated reactor 2 is 0.5～2L, and maximum operation (service) temperature is 400～500 ℃, and maximum working pressure (MOP) is 30.0～40.0Mpa.The magnetic stirring apparatus maximum speed is 700～800r/min.Condenser 3 adopts coil pipe water-cooled refrigeratory, and heat eliminating medium adopts tap water.Counterbalance valve 4 is made up of high pressure counterbalance valve, high-pressure hand pump and back pressure buffer container, controlled pressure scope: 0～40MPa.The light source 5 that adopts is an xenon source, and single beam has reference beam, holographic grating, and wavelength accuracy 2mm can obtain the all-wave long data of 200nm to 1000nm.
Optical fiber 6 is the holographic online transmission technology of optical fiber, comprises highly sensitive fiber spectrometer, has high sensitivity, and high quantization efficiency and HDR not only can detect visible light, can also respond to the deep ultraviolet wave band (～185-300nm).Front end is placed a kind of spectrophotometer with fiber optic transmission detection light intensity by in the quartz glass tunnel, comprises entrance slit, concave grating and detector with source imaging.
Ccd array detecting device 7 is more ripe technically than traditional U VVIS spectrophotometer, and more general, reliable and succinct.The instantaneous completion of whole spectra collection also is stored in the computing machine, the most general linear CCD array format 2048 pixel CCD of employing.Highly sensitive, low noise CCD has 2048 or 3648 pixels.
Temperature, pressure probe 8 is sensor-type probe, can be meant that with output result 9 all kinds of parameters are transferred in the outside computer that is connected by the software real-time analysis through signal converter through data collecting card Information Monitoring software.
The operational scheme of this method is:
By volume pump 1 organic wastewater and oxygenant thereof are squeezed into agitated reactor 2; Volume pump 1 injection scope reaches 0-50MP; Reactive material is flowed out after condenser 3 condensations through counterbalance valve 4 outflows by agitated reactor 2 after reacting; Wherein by counterbalance valve 4 may command entire reaction still internal pressures height, range of control is 0-40MP, constitutes a cover serialization consersion unit thus; Agitated reactor 2 is in service; Light by light source 5 emission wavelength ranges 200 to 1000nm wavelength imports in agitated reactor 2 bodies through resistant to elevated temperatures optical fiber 6 holographic transmission mechanisms; Optical fiber 6 is as signal coupler spare simultaneously; With the tested spectrometer that couples light in the optical fiber 6; Use ccd array spectrophotometer 7 and optical fiber 6 to be used simultaneously to obtain to be transferred to external computer through signal converter after the relevant real time data of experiment and to carry out software and interpretation of result 9, simultaneous temperature pressure probe 8 obtains data can analyze also input results 9 through conversion of signals entering software at any time.
Through supercritical reaction still observation and control technology of the present invention, the breakthrough of core technologies such as full spectrum on line detection technique, and carry out the integrated innovation of electromechanical integration, develop novel scientific research apparatus equipment; Be used to find the new phenomenon of supercritical water reaction process, can explain the supercritical water reaction energy level variations, catalytic activity, new rule such as synthesis mechanism; Obtain the order of reaction of multiple supercritical water reaction, rate constant, energy of activation, pre-exponential factor; Entropy Changes, important foundation data such as enthalpy change, and this is for material, oil; Chemical industry, electric power, the scientific research in fields such as environmental protection will have crucial facilitation.
Technical scheme provided by the invention is: in autoclave, feed light source, through holographic online transmission technology of optical fiber and ccd array spectrophotometer technology, monitor the DO in the supercritical water reaction process in real time; PH, temperature, pressure; Conductivity, the Millisecond Changing Pattern of data such as spectrum.Its core technology is being used of holographic spectrum on line transmission mechanism of optical fiber and ccd array spectrophotometer technology, mainly adopts fiber optics as for signal coupler spare, with the tested spectrometer that couples light to, uses CCD and photoelectron diode array detector simultaneously.
Claims (7)
1. the investigating method of a supercritical water reaction still; It is characterized in that; This method combines fiber spectrum on-line analysis and ccd array spectrophotometric measuring technology that the supercritical water reaction still is carried out real-time on-line monitoring; Specifically may further comprise the steps: the supercritical water reaction still is when operation; Light by light emitted wavelength coverage 200-1000nm wavelength imports in the reaction kettle body through the holographic transmission mechanism of resistant to elevated temperatures optical fiber, and optical fiber is as signal coupler spare, with the tested spectrometer that couples light in the optical fiber; Use ccd array spectrophotometer and optical fiber to be used to obtain to be transferred to external computer through signal converter after the relevant real time data of experiment and to carry out software and interpretation of result, the temperature, pressure probe obtains data and passes through conversion of signals entering software and interpretation of result.
2. the investigating method of a kind of supercritical water reaction still according to claim 1; It is characterized in that; The reaction volume of described supercritical water reaction still is 0.5～2L; Maximum operation (service) temperature is 400～500 ℃, and maximum working pressure (MOP) is 30.0～40.0Mpa, and the magnetic stirring apparatus maximum speed that agitated reactor uses is 700～800r/min.
3. the investigating method of a kind of supercritical water reaction still according to claim 1 is characterized in that, described light source is an xenon source, and single beam has reference beam, holographic grating, and wavelength accuracy 2mm can obtain the all-wave long data of 200-1000nm.
4. the investigating method of a kind of supercritical water reaction still according to claim 1; It is characterized in that; The holographic transmission mechanism of described optical fiber adopts highly sensitive fiber spectrometer to carry out detected transmission, is provided with the spectrophotometer that detects light intensity with fiber optic transmission in the quartz glass tunnel of fiber spectrometer front end.
5. the investigating method of a kind of supercritical water reaction still according to claim 4 is characterized in that, described spectrophotometer comprises the entrance slit of source imaging, concave grating and detector.
6. the investigating method of a kind of supercritical water reaction still according to claim 1 is characterized in that, described ccd array spectrophotometric is counted linear CCD array format 2048 pixel CCD.
7. the investigating method of a kind of supercritical water reaction still according to claim 1 is characterized in that, described temperature, pressure probe is for sensor-type probe, through data collecting card collecting temperature pressure information.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489094A (en) * | 2016-01-07 | 2016-04-13 | 清华大学 | Subcritical, supercritical pressure, temperature and phase state teaching experiment bench |
| CN105641968A (en) * | 2016-01-07 | 2016-06-08 | 中国原子能科学研究院 | Supercritical fluid complex reaction device with online spectrum monitoring function |
| CN111693526A (en) * | 2020-05-19 | 2020-09-22 | 西安交通大学 | Crude oil dissolution observation device in supercritical water and dissolution degree detection method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489094A (en) * | 2016-01-07 | 2016-04-13 | 清华大学 | Subcritical, supercritical pressure, temperature and phase state teaching experiment bench |
| CN105641968A (en) * | 2016-01-07 | 2016-06-08 | 中国原子能科学研究院 | Supercritical fluid complex reaction device with online spectrum monitoring function |
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| CN105641968B (en) * | 2016-01-07 | 2018-04-17 | 中国原子能科学研究院 | A kind of supercritical fluid complex reaction device with online spectrum monitoring |
| CN111693526A (en) * | 2020-05-19 | 2020-09-22 | 西安交通大学 | Crude oil dissolution observation device in supercritical water and dissolution degree detection method |
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Application publication date: 20121003 |