CN102172503A - Device for researching transfer-reaction in ionic liquid-supercritical fluid in situ - Google Patents
Device for researching transfer-reaction in ionic liquid-supercritical fluid in situ Download PDFInfo
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- CN102172503A CN102172503A CN2011100384722A CN201110038472A CN102172503A CN 102172503 A CN102172503 A CN 102172503A CN 2011100384722 A CN2011100384722 A CN 2011100384722A CN 201110038472 A CN201110038472 A CN 201110038472A CN 102172503 A CN102172503 A CN 102172503A
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Abstract
The invention provides an ionic liquid and supercritical fluid coupled reaction, separation and analysis integrated device. The device can simultaneously complete unit operations such as reaction and supercritical fluid extraction under the rigorous (high temperature, high pressure and high corrosivity) and continuous conditions, reaction behaviours in a reaction phase and a separation phase are recorded by virtue of a real-time imaging system, and an infrared in situ analytical instrument, a laser scattering device and a chromatograph are integrated; and meanwhile, automatic control on the whole system is realized. The device concretely comprises a raw material supply system, a reactor, a monitoring and component analysis system and an operating parameter monitoring and control system. The device adopts a sapphire as a window, and phase state and reaction conditions in the reactor can be directly observed and recorded under the conditions of high temperature and high pressure.
Description
Technical field:
The present invention relates to the coupling of a kind of ionic liquid and supercritical fluid reaction, separate and analyze integrated automatic research device, this device can be used for the coupling integrated research of reaction, extract and separate in chemical industry or the energy field related process.
Background technology:
Just find that as far back as 19th century people supercritical fluid has great solvability.It is found that the fluid phenomenon that dissolving increases to organic compound that is in more than critical pressure and the critical-temperature is very surprising.Generally can increase several magnitude, under proper condition even can reach by vapour pressure and calculate more than 1000 times of gained concentration.Supercritical fluid is widely used in the chemical process as reaction medium, reactant etc.
Ionic liquid has become the forward position and the focus of International Technology as novel reaction medium or catalyst, have not volatile, room temperature is in a liquid state, structure and polarity are adjustable, the characteristic that has solvent and catalyst function concurrently, wide application potential and prospect have been showed, for great technology/process breaks through and innovation provides new opportunity.
Being coupled as chemical reaction, transmitting great application prospect is provided of ionic liquid and supercritical fluids system.Existing overcritical device all can't by Real Time Image System and monitoring system registers reacting phase with separate mutually in the reaction carried out, can't systematic research ionic liquid-supercritical fluid system to the invigoration effect of reaction, can't be optimized reaction system in real time.In addition, business-like overcritical device all is at certain class fluid or certain class reaction design, can not transplant in ionic liquid-supercritical fluid system, comprehensively the universality rule of this system of research evaluation.Therefore, parsing ionic liquid-supercritical fluid to the facilitation of reaction and the details of alternate substance transfer, becomes the precondition of industrial applications when reaction.With the advantages of ionic liquid and supercritical fluid,, can utilize the characteristic of ionic liquid and supercritical fluid, continuously the extract and separate product with the perfect medium of ionic liquid/supercritical fluid two-phase system as homogeneous chemical reaction.Desirable ionic liquid-supercritical fluids system chemical reaction is the homogeneous reaction of finishing in the two-phase system.According to ionic liquid and supercritical fluid to reactant, the different dissolubilities of product and catalyst, ionic liquid mutually with supercritical fluid two kinds of media that do not dissolve each other mutually, or supercritical fluid can be partially dissolved in ionic liquid mutually and ionic liquid is insoluble to supercritical phase mutually, ionic liquid is as catalyst or reaction medium, chemical reaction is finished in mutually at ionic liquid, and reacted product then goes out the ionic liquid phase by the supercritical fluid continuous extraction.Ionic liquid can not be dissolved in supercritical phase, thereby has avoided ion liquid loss and to the pollution of product.This process can also reduce the ionic liquid concentration of middle product mutually, and chemical balance is moved to the product direction, has increased the yield of reactant.In addition, this method is effective especially for the heat-sensitive substance that separates difficult volatilization from ionic liquid.Help the separation of product, the separation and the regeneration of catalyst, thereby improve reaction efficiency greatly.
Existing overcritical equipment has supercritical extraction unit, overcritical particulate preparation facilities, supercritical water oxidation device, supercritical fluid reaction system, the checkout gear that balances each other, hydrate reaction device etc.But these devices all can't by Real Time Image System and monitoring system registers reacting phase with separate mutually in the reaction carried out, can't systematic research ionic liquid-supercritical fluid system to the invigoration effect of reaction, can't be optimized (Seda Keskin to reaction system in real time, et al., J.of SupercriticalFluids, 2007,43:150; CN1403769).In addition, business-like overcritical device all is at certain class fluid or certain class reaction design, can not transplant in ionic liquid-supercritical fluid system, comprehensively the universality rule of this system of research evaluation.
The overcritical equipment that can be operated in addition under the HTHP is limit owing to material, can not satisfy direct-recording requirement, all can't have enough intensity under HTHP as tempered glass and quartz glass etc.Business-like overcritical equipment generally can only be in lower temperature and pressure (200 ℃ 20MPa) be descended direct tape deck interior reaction and phase transformation situation.The present invention adopts sapphire as transparent medium, and the compound forms seal means of graphite and stainless steel reaches target.This design can be up to 350 ℃ in temperature, and pressure is up under the condition of 40MPa and works.
The present invention can be used for obtaining ionic liquid as reaction medium or catalyst, and supercritical fluid is as the general character scientific law of the coupling process of separating medium.This device can be finished unit operations such as reaction and supercritical fluid extraction in the ion liquid medium simultaneously under harsh (HTHP and highly corrosive) and the condition of continuity, by Real Time Image System record reacting phase with the reflex action of carrying out in separating mutually, and integrated infrared in-situ analyzer device, laser light scattering device, chromatograph etc. have been realized system-wide automatic control simultaneously.For further investigation ionic liquid-supercritical fluid system provides research platform in the unique advantage aspect reaction-extraction-separation.
Summary of the invention:
The present invention relates to the coupling of a kind of ionic liquid and supercritical fluid reaction, separate and analyze integrated automatic research device, this device can be finished unit operations such as reaction and supercritical fluid extraction in the ion liquid medium simultaneously under harsh (HTHP and highly corrosive) and the condition of continuity, by Real Time Image System record reacting phase with the reflex action of carrying out in separating mutually, and integrated infrared in-situ analyzer device, laser light scattering device, chromatograph etc. have been realized system-wide automatic control simultaneously.This device can be used for the coupling integrated research of reaction, extract and separate in chemical industry or the energy field related process.
In order better to realize purpose of the present invention, the creationary utilization original position of designer analysis means, in conjunction with transparent sapphire window behavior of inside reactor fluid and reflex action are observed, carry out online real-time data acquisition, analysis by the spectrum means that equipment is integrated, realize reaction and the online real-time optimization that separates.This device can be under exacting terms (high temperature and high pressure), finish ionic liquid mutually in the product of chemical reaction and supercritical fluid phase separate, avoid conventional separation energy consumption height, easily cause the problem of cross pollution and reactant recovery difficulty.
Below in conjunction with accompanying drawing, describe content of the present invention in detail.
Concrete structure of the present invention mainly comprises sampling system, elemental analysis system, real-time analyzer, operational factor monitor control system as shown in Figure 1, multiple step format decompression separation device and reactant/compositions such as medium recovery system.Describe respectively below.
1. raw material supply system.The sample introduction of ionic liquid and fluid is finished by the pulse free high-pressure pump NP-KX550 that can produce constant flow, its maximum working pressure is 40MPa, flow can be adjustable on a large scale at 0.01-50ml/min, adopted the stepper motor of microcomputer control at drive division, adopt digital control, can finish common gas and liquid, as the sample introduction of hydrogen, nitrogen, oxygen, carbon dioxide, alcohols, hydro carbons, water, ethers, lipid, ketone, aldehydes fluid.
2. ionic liquid-supercritical fluid reactor.This reactor should be able to be under conventional and unconventional condition (400 ℃ of high temperature, high pressure 40MPa), in the different ionic liquid medium, react with product and shift original position research, so high temperature resistant (temperature range: 25～400 ℃ of reactor of the present invention, precision: ± 1 ℃), high pressure (pressure limit 0.1～40MPa, precision: ± 0.1%), corrosion-resistant, the heater chuck is arranged outward, kettle is the plug-in type heating system, a whole set of heating system is controlled automatically by instrument, and has a temperature alarm, of paramount importance is under HTHP the inside reactor states of matter to be write down and observe in order to finish, this reactor has the sapphire window that is installed in diverse location, reaches target by graphite and the compound forms seal means of stainless steel.In addition, also have charging and discharging opening, thermocouple, pressure sensor etc.
3. monitor and imaging system.By monitoring and imaging system, see through sapphire transparent medium on the reactor, by record reactor inner cases such as integrated advanced analysis detection system laser light scattering device and high-speed cameras; This system has functions such as image real-time acquisition, demonstration, storage.
4. composition on-line analysis.Mainly finish the online direct qualitative detection of reactant and product, the qualitative and quantitative analysis of gaseous component, finish by Agilent gas chromatograph and Fourier infrared spectrograph, liquid phase component passes through liquid chromatogram, Raman spectrometer carries out off-line analysis, and can bear HTHP and realize continuous-flow, also, adopt special material and specification according to the characteristics of online analytical instrument.Not only satisfy the reaction requirement but also satisfy spectrum, heat on-line analysis requirement.
5. data automatic collecting and control.Data automatic collecting and control realize by computer integrated data acquisition system and control software, the physical-chemical parameters such as temperature, pressure and flow etc. are converted into the data signal Input Software by sensor and conversion equipment, and by control system various parameters are regulated and control, gather numeral and handle by parallel device and optimize.
Description of drawings:
Accompanying drawing 1 is the overall structure that the original position research device is transmitted in reaction in ionic liquid-supercritical fluid;
Accompanying drawing 2 is the front view of main reactor.
Accompanying drawing 3 is the vertical view of main reactor.
Accompanying drawing 4 is the side view of main reactor.
Innovative point of the present invention is by special transparent medium as form, directly observe and the record HTHP under inside reactor chemical reaction and phase transformation, successfully solved record and observe that ionic liquid separates with continuous extraction under the supercritical fluid HTHP, chemical reaction and phase transition phenomena.
The specific embodiment:
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
1. the design of main reactor and manufacturing.DESIGN OF REACTOR figure as shown in Figure 2.High temperature resistant, the high pressure of reactor and the corrosion resistance of design are strong.Employing can be heat-resisting withstand voltage and corrosion resistant nickel-base alloy as the material of main part of reactor.Thickness is that the sapphire of 3cm writes down the inside reactor states of matter under HTHP as transparent medium and observes, all sapphire glass is fixed on the reactor by flange with intensity under the HTHP and stability than more excellent graphite and the multi-stage sealed means of metal washer, the heater chuck is arranged outward, kettle is the plug-in type heating system, a whole set of heating system is controlled automatically by instrument, and has temperature alarm.Reactor one side has 2 injection ports, leaves 2 and an outlet in an other side and bottom respectively.Product is cooled off through recirculated water by cooling coil by after the outlet.The reactor internal pressure is regulated by the counterbalance valve that is connected behind the cooling coil.In order further to guarantee the security of reactor, realize overvoltage automatically unloading function simultaneously by taking the overvoltage automatic safety device on reactor.
Claims (7)
1. the reaction of an ionic liquid and supercritical fluid coupling, separate and analyze integrated automatic research device, it is characterized in that:
(1) described device can be finished reaction and supercritical fluid extraction unit operations in the ion liquid medium simultaneously under high temperature, high pressure, highly corrosive and the condition of continuity; (2) by Real Time Image System record reacting phase with the reflex action in separating mutually;
(3) integrated infrared in-situ analyzer device, laser light scattering device and gas chromatograph equipment.
2. device according to claim 1 is characterized in that device is made of following system: (1) raw material supply system; (2) reaction system; (3) composition on-line analysis system; (4) operational factor monitoring and control system; (5) detection and imaging system; (6) multiple step format decompression separation system; (7) product recovery system.
3. device according to claim 2, it is characterized by the raw material supply system is finished by the pulse free high-pressure pump, its maximum working pressure is 40MPa, finish common gas and liquid, as the sample introduction of hydrogen, nitrogen, oxygen, carbon dioxide, alcohols, hydro carbons, water, ethers, lipid, ketone, aldehydes fluid.
4. device according to claim 2 is characterized by reactor body and is made of nickel-base alloy corrosion-resistant, high temperature resistant, high pressure, and the transparent medium of its visual form is the sapphire material, and sealed material is selected graphite and stainless steel composite material for use.
5. device according to claim 2, it is characterized by the reflex action monitoring finishes by imaging system, the inside reactor phase is passed through visual form record, image real-time acquisition, demonstration, storage by integrated advanced analysis detection system laser light scattering device and high-speed camera.
6. device according to claim 2, it is characterized by reactant and product gaseous component finishes by Agilent gas chromatograph and Fourier infrared spectrograph on-line analysis system, liquid phase component is by liquid chromatogram, and Raman spectrometer carries out off-line analysis to be finished.
7. device according to claim 1, it is characterized by described device working pressure scope is 0.1～40MPa, precision is ± 0.1%; Temperature range is 25～400 ℃, and precision is ± 1 ℃.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102706812A (en) * | 2012-05-31 | 2012-10-03 | 上海交通大学 | Measurement and control method of supercritical water reaction kettle |
| CN103196861A (en) * | 2013-03-29 | 2013-07-10 | 西安交通大学 | Flowing high temperature and high pressure phase equilibrium measuring device and application method thereof |
| CN103196963A (en) * | 2012-01-05 | 2013-07-10 | 中国科学院过程工程研究所 | Ionic liquid system electrochemical process in-situ research device |
| CN103424305A (en) * | 2013-08-08 | 2013-12-04 | 江南大学 | Device used for monitoring biological sample treatment and/or biochemical reaction under ultrahigh pressure on line and in situ |
| CN103712931A (en) * | 2013-12-31 | 2014-04-09 | 陕西师范大学 | High-pressure ultraviolet visible near-infrared spectroscopy device for online monitoring of supercritical system |
| CN104888493A (en) * | 2015-06-05 | 2015-09-09 | 海正药业(杭州)有限公司 | Device for realizing liquid-liquid extraction separation self-control through electric conduction and method thereof |
| 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 |
| CN109932334A (en) * | 2019-04-01 | 2019-06-25 | 中国科学院过程工程研究所 | A kind of multi-functional dynamic analysis system of chemical process |
| CN111707333A (en) * | 2020-07-08 | 2020-09-25 | 南通市海视光电有限公司 | Intelligent sight glass liquid phase detection system |
| CN114544618A (en) * | 2020-11-25 | 2022-05-27 | 扬州华宝石油仪器有限公司 | Bubble monitor capable of resisting high temperature and high pressure |
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| CN201124092Y (en) * | 2007-11-27 | 2008-10-01 | 中国科学院化学研究所 | Above-critical state continuous chemical reaction device |
| CN101363821A (en) * | 1996-02-28 | 2009-02-11 | 休斯顿大学 | Catalyst testing process and apparatus |
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| CN101363821A (en) * | 1996-02-28 | 2009-02-11 | 休斯顿大学 | Catalyst testing process and apparatus |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103196963A (en) * | 2012-01-05 | 2013-07-10 | 中国科学院过程工程研究所 | Ionic liquid system electrochemical process in-situ research device |
| CN102706812A (en) * | 2012-05-31 | 2012-10-03 | 上海交通大学 | Measurement and control method of supercritical water reaction kettle |
| CN103196861A (en) * | 2013-03-29 | 2013-07-10 | 西安交通大学 | Flowing high temperature and high pressure phase equilibrium measuring device and application method thereof |
| CN103196861B (en) * | 2013-03-29 | 2014-12-10 | 西安交通大学 | Flowing high temperature and high pressure phase equilibrium measuring device and application method thereof |
| CN103424305A (en) * | 2013-08-08 | 2013-12-04 | 江南大学 | Device used for monitoring biological sample treatment and/or biochemical reaction under ultrahigh pressure on line and in situ |
| CN103712931B (en) * | 2013-12-31 | 2016-08-17 | 陕西师范大学 | The high pressure UV, visible light near infrared light spectral apparatus of on-line monitoring supercritical fluids system |
| CN103712931A (en) * | 2013-12-31 | 2014-04-09 | 陕西师范大学 | High-pressure ultraviolet visible near-infrared spectroscopy device for online monitoring of supercritical system |
| CN104888493A (en) * | 2015-06-05 | 2015-09-09 | 海正药业(杭州)有限公司 | Device for realizing liquid-liquid extraction separation self-control through electric conduction and method thereof |
| 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 |
| 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 |
| CN109932334A (en) * | 2019-04-01 | 2019-06-25 | 中国科学院过程工程研究所 | A kind of multi-functional dynamic analysis system of chemical process |
| CN111707333A (en) * | 2020-07-08 | 2020-09-25 | 南通市海视光电有限公司 | Intelligent sight glass liquid phase detection system |
| CN114544618A (en) * | 2020-11-25 | 2022-05-27 | 扬州华宝石油仪器有限公司 | Bubble monitor capable of resisting high temperature and high pressure |
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Application publication date: 20110907 |