CN105776144A - Two phase transfer system-based singlet state oxygen generation method - Google Patents
Two phase transfer system-based singlet state oxygen generation method Download PDFInfo
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- CN105776144A CN105776144A CN201410787667.0A CN201410787667A CN105776144A CN 105776144 A CN105776144 A CN 105776144A CN 201410787667 A CN201410787667 A CN 201410787667A CN 105776144 A CN105776144 A CN 105776144A
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Abstract
The invention relates to a singlet state oxygen generation method, and belongs to the technical field of chemical oxygen-iodine lasers. The method comprises the following steps: mixing an alkaline ionic liquid insoluble in water with an aqueous hydrogen peroxide solution to form a two phase transfer system, and reacting the transferred ionic liquid phase with chlorine to generate singlet state oxygen in order to realize water and singlet state oxygen isolation. The method is helpful for reducing the quenching effect of water on singlet state oxygen, and reduces the content of water in the singlet state oxygen, and the alkaline ionic liquid has an enrichment effect on hydrogen peroxide to make effective solving of the bottleneck problem of hydrogen peroxide concentration restriction in the raw material regeneration process of chemical oxygen-iodine lasers under traditional technological conditions be possible, so the method is of great significance to improve the singlet state oxygen yield of the chemical oxygen-iodine lasers, reduce the water content of the singlet state oxygen and solve the raw material regeneration problem.
Description
Technical field
The present invention relates to the production method of creating singlet oxygen by using in a kind of COIL, specifically a kind of creating singlet oxygen by using production method based on alkali ionic liquid-aqueous hydrogen peroxide solution two phase transfer system.
Background technology
COIL is the currently the only chemical laser successfully operating at electron state transition, and wavelength is 1.315 μm, is placed exactly in atmospheric window, has a good application prospect in many aspects, thus obtains and pay attention to widely.
Creating singlet oxygen by using (O2(1Δ)) as the energy source of oxygen-iodine chemical laser, the dissociating of iodine, pumping pass the processes such as energy have and directly affect, its concentration determines the important technology indexs such as COIL chemical efficiency to a certain extent, and can even determine laser instrument runs by normal table.Therefore, the acquisition of creating singlet oxygen by using is one of matter of utmost importance encountered in COIL research, design process.
Although the production method of creating singlet oxygen by using has multiple at present, such as chlorine and the gas-liquid reaction method of alkaline hydrogen peroxide solution, chlorine and solid peroxide or the gas-solid reaction method of superoxides, fullerene Photosensitive reaction method etc., currently, the main of practicality or gas-liquid reaction method have been obtained.This is primarily due to the creating singlet oxygen by using that gas-liquid reaction method can be stablized, obtain high absolute concentration quickly, in large quantities, meets the demand of COIL.
But, traditional gas-liquid system there is also some obvious shortcomings, wherein the most serious be exactly participate in the alkaline hydrogen peroxide solution of reaction can by substantial amounts of water (H2O) bring in laser instrument.These H2First O is carried along in Oxygen Generator by BHP, at BHP and chlorine (Cl2) between occur reaction heat effect under, being extremely easy to be transferred in the gas phase of Oxygen Generator, being brought into the oxygen iodine mixing section that COIL is follow-up further, thus result in water (H2O) ubiquity in the laser.There are some researches show, hydrone (H2O) a large amount of ubiquities in the laser are to cause the key factor of the serious quencher of active specy in COIL.This is because, H2In O molecule, the vibration level of H-OH key is close with active specy (including creating singlet oxygen by using and active iodine atom) resonance biography energy energy level, and active specy is prone to energy is reached H2O and return to ground state, thus causing the serious quencher of active specy.
For the problems referred to above, a kind of solution is will to be likely to occur H in reaction system2The place of O is with heavy water (D2O) substitute, namely adopt so-called alkalescence deuterium-peroxide (BDP) solution to replace BHP, this makes it possible to avoid H2The O quenching effect to active specy.Because utilizing D2O replaces H2O does not change the chemical reaction characteristic of water, but owing to the atomic mass of D is different from H, wherein the vibration level of D-OD and H2In O there is larger difference in the vibration level of H-OH and active specy, thus the resonance avoided between active specy and water passes the inactivation that can cause.Result of study confirms, at H2O in O2(1Δ) the survival life-span be 3.8 μ s, and at D2In O, this time is extended to 62 μ s (A.AGorman, Singletoxygen, inCRCHandbookofOrganicPhotochemistry, Vol.II (J.C.ScaianoEd.), CRCpress, BocaRaton, FL, p.229-247,1989), D2The quenching effect of active iodine species is H by O steam2O steam 1/50 (J.Chem.Phys.Vol.64, No.4, p.1850,1976).
But, above-mentioned solution is greatly improved the operating cost of COIL.Heavy water abundance in nature is relatively low, and its extraction cost is high, routinely supply channel, and the heavy water price of 99.9D.% reaches about ten thousand yuan per kilograms, and this makes the operating cost of COIL become to be difficult to accept.
If it is possible to find a kind of new reaction system, the high-efficient characteristic of gas-liquid reaction system can be kept, be avoided that again H2O is to the harmful effect of active specy in COIL, then a kind of desirably creating singlet oxygen by using of can yet be regarded as produces system.
Summary of the invention
The present invention is analyzing on the basis of existing creating singlet oxygen by using generation system and method, it is proposed that a kind of two phase transfer systems for producing creating singlet oxygen by using, and the creating singlet oxygen by using based on this system produces new method.Basic process is as follows: a) being placed in same raw material storage tanks by alkali ionic liquid R. [OH], aqueous hydrogen peroxide solution, wherein R represents the cation group of alkali ionic liquid；B) mix and blend, now R. [OH] from aqueous hydrogen peroxide solution mutually absorb hydrogen peroxide, hydrogen peroxide reacts with R. [OH] and is converted into R. [O2H], eventually form containing R. [O2H] the two-phase system that coexists of ionic liquid phase and water-soluble liquid phase；C) being extracted mutually by ionic liquid to singlet oxygen generator and chlorine reaction, generator exports can obtain creating singlet oxygen by using, other two kinds of product hydrogen peroxide, R. [Cl] and the unreacted R. [O completely that will obtain2H] return in the described raw material storage tanks of step a), hydrogen peroxide will automatically into aqueous hydrogen peroxide solution phase, and R. [Cl] and unreacted R. [O completely2H] ionic liquid phase will be entered.
Continuously ionic liquid is extracted to singlet oxygen generator and chlorine reaction mutually, along with the ionic liquid carried out in the raw material storage tanks middle R. [O mutually of reaction2H] concentration is gradually reduced.Until the ionic liquid middle R. [O mutually in raw material storage tanks2H] lowering of concentration is to setting the process stopping step c) after endpoint concentration；At aqueous hydrogen peroxide solution middle insertion two electronics oxygen reduction cathodes mutually, ionic liquid is the middle analysis chlorine anode that inserts mutually, and energising electrolysis, R. [Cl] is converted R. [OH], the recyclable recycling of chlorine again, and in water-soluble liquid phase, concentration of hydrogen peroxide is promoted recovery；Can again repeat the process of step c), creating singlet oxygen by using can be continuously available.Described alkali ionic liquid is water-fast ionic liquid, described alkali ionic liquid can form two phase stratification with aqueous hydrogen peroxide solution, in described alkali ionic liquid, R group is strong hydrophobic group, and R is that at least one replaces imidazoles or the pyridine anionic group that position is replaced by the above fluorinated alkyl of the six above alkyl of carbon or three carbon.R.[O2H] endpoint concentration is arbitrary concrete concentration in 3～5mol/L interval.Aqueous hydrogen peroxide solution concentration, more than 1mol/L, is further preferably greater than 3mol/L.
The method has the advantage that
(1) alleviating creating singlet oxygen by using quencher in the liquid phase, the design for Oxygen Generator provides more loose constraints.Ionic liquid is absent from H-OH key, and in theory, the creating singlet oxygen by using time-to-live therein will be significantly increased, and it reduce the requirement to Oxygen Generator.
(2) existence of steam in Oxygen Generator is decreased.Containing substantial amounts of water in traditional BHP, inevitably it is brought in gas phase when BHP is with chlorine reaction, is entrained further among laser instrument subsequent sections, the operation of laser instrument is caused serious harmful effect.Novel two-phase system, enters the only R. [O of generator2H], it is absent from the interference of water.
(3) raw material service efficiency is high, R. [OH] and H2O2Binding ability is strong, to H2O2There is enrichment so that peroxide is concentrated, under comparable sodium Sharp criteria, improve the service efficiency of raw material.
(4) technical difficulty of raw material regeneration is reduced.Currently, the chemical raw material regeneration techniques of COIL remains certain technical bottleneck, is exactly mainly that peroxide concentrations is difficult to reach laser instrument instructions for use.When the method, due to R. [OH] and H2O2Binding ability is strong, reduces the requirement that hydrogen peroxide regenerates concentration, is expected to so that raw material regeneration techniques bottleneck is solved smoothly.
Accompanying drawing explanation
Fig. 1 is flow process and the schematic diagram that two phase transfer systems produce creating singlet oxygen by using.
Detailed description of the invention:
Embodiment 1
By 1 kilogram of alkali ionic liquid C3F7ImCH3. the aqueous hydrogen peroxide solution that [OH], 1 kilogram of concentration are 5mol/L is placed in raw material storage tanks and mix and blend, now C3F7ImCH3. [OH] from aqueous hydrogen peroxide solution mutually absorb hydrogen peroxide, C3F7ImCH3. [OH] generates C with hydroperoxidation3F7ImCH3.[O2H], eventually form containing C3F7ImCH3.[O2H] the two-phase system that coexists mutually with aqueous hydrogen peroxide solution of ionic liquid phase；Being extracted mutually by ionic liquid to Small Jet formula singlet oxygen generator and chlorine reaction, generator exports can obtain creating singlet oxygen by using, other two kinds of product hydrogen peroxide, the C that will obtain3F7ImCH3. [Cl] and unreacted C completely3F7ImCH3.[O2H] return in raw material storage tanks, hydrogen peroxide will automatically into aqueous hydrogen peroxide solution phase, and C3F7ImCH3. [Cl] and unreacted C completely3F7ImCH3.[O2H] ionic liquid phase will be entered；Use continuously, until ionic liquid middle C mutually3F7ImCH3.[O2H] lowering of concentration stops to 3.7mol/L；At aqueous hydrogen peroxide solution middle graphite cathode mutually, ionic liquid is middle mutually inserts analysis chlorine DSA anode, and be energized electrolysis, C3F7ImCH3. [Cl] is converted C again3F7ImCH3.[O2H], the recyclable recycling of chlorine, and aqueous hydrogen peroxide solution middle concentration of hydrogen peroxide mutually is promoted recovery.
Claims (5)
1. the creating singlet oxygen by using production method based on two phase transfer systems, it is characterised in that process is as follows:
A) being placed in same raw material storage tanks by alkali ionic liquid R. [OH], aqueous hydrogen peroxide solution, wherein R represents the cation group of alkali ionic liquid；
B) mix and blend, now R. [OH] from aqueous hydrogen peroxide solution mutually absorb hydrogen peroxide, hydrogen peroxide reacts with R. [OH] and is converted into R. [O2H], eventually form containing R. [O2H] the two-phase system that coexists of ionic liquid phase and water-soluble liquid phase；
C) being extracted mutually by ionic liquid to singlet oxygen generator and chlorine reaction, generator exports can obtain creating singlet oxygen by using, other two kinds of product hydrogen peroxide, R. [Cl] and the unreacted R. [O completely that will obtain2H] return in the described raw material storage tanks of step a), hydrogen peroxide will automatically into aqueous hydrogen peroxide solution phase, and R. [Cl] and unreacted R. [O completely2H] ionic liquid phase will be entered；Continuously ionic liquid is extracted to singlet oxygen generator and chlorine reaction mutually, along with the ionic liquid carried out in the raw material storage tanks middle R. [O mutually of reaction2H] concentration is gradually reduced.
2. according to claim 1 based on the creating singlet oxygen by using production method of two phase transfer systems, it is characterised in that: until the ionic liquid middle R. [O mutually in raw material storage tanks2H] lowering of concentration is to setting the process stopping step c) after endpoint concentration；At aqueous hydrogen peroxide solution middle insertion two electronics oxygen reduction cathodes mutually, ionic liquid is the middle analysis chlorine anode that inserts mutually, and energising electrolysis, R. [Cl] is converted R. [OH], the recyclable recycling of chlorine again, and in water-soluble liquid phase, concentration of hydrogen peroxide is promoted recovery；Can again repeat the process of step c), creating singlet oxygen by using can be continuously available.
3. according to claim 1 based on the creating singlet oxygen by using production method of two phase transfer systems, it is characterized in that: described alkali ionic liquid is water-fast ionic liquid, described alkali ionic liquid can form two phase stratification with aqueous hydrogen peroxide solution, in described alkali ionic liquid, R group is strong hydrophobic group, and R is that at least one replaces imidazoles or the pyridine anionic group that position is replaced by the above fluorinated alkyl of the six above alkyl of carbon or three carbon.
4. according to claim 2 based on the creating singlet oxygen by using production method of two phase transfer systems, it is characterised in that: R. [O2H] endpoint concentration is arbitrary concrete concentration in 3～5mol/L interval.
5. according to claim 1 based on the creating singlet oxygen by using production method of two phase transfer systems, it is characterised in that: aqueous hydrogen peroxide solution concentration, more than 1mol/L, is further preferably greater than 3mol/L.
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Cited By (7)
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| EP3323779A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Method for generating oxygen using ionic liquids for decomposing peroxides |
| EP3323783A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Use of ionic liquids in compositions for generating oxygen |
| EP3323471A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Device for generating oxygen |
| EP3323781A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Method for generating oxygen from compositions comprising ionic liquids |
| EP3323782A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Oxygen generating compositions comprising ionic liquids |
| EP3323780A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Compositions comprising ionic liquids and peroxides |
| EP3323470A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Oxygen generator using ionic liquids |
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Cited By (21)
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| EP3323779A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Method for generating oxygen using ionic liquids for decomposing peroxides |
| EP3323783A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Use of ionic liquids in compositions for generating oxygen |
| EP3323471A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Device for generating oxygen |
| EP3323781A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Method for generating oxygen from compositions comprising ionic liquids |
| EP3323782A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Oxygen generating compositions comprising ionic liquids |
| EP3323780A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Compositions comprising ionic liquids and peroxides |
| EP3323470A1 (en) * | 2016-11-18 | 2018-05-23 | Goodrich Lighting Systems GmbH | Oxygen generator using ionic liquids |
| CN108069394A (en) * | 2016-11-18 | 2018-05-25 | 古德里奇照明系统有限责任公司 | For by the method for the composition generation oxygen comprising ionic liquid |
| CN108069399A (en) * | 2016-11-18 | 2018-05-25 | 古德里奇照明系统有限责任公司 | For using the oxygen generator of ionic liquid |
| CN108069395A (en) * | 2016-11-18 | 2018-05-25 | 古德里奇照明系统有限责任公司 | Purposes of the ionic liquid in the composition for generating oxygen |
| CN108069398A (en) * | 2016-11-18 | 2018-05-25 | 古德里奇照明系统有限责任公司 | Use the method for ionic liquid peroxynitrite decomposition compound |
| CN108069396A (en) * | 2016-11-18 | 2018-05-25 | 古德里奇照明系统有限责任公司 | Include the composition of the ionic liquid for peroxynitrite decomposition compound |
| US10544044B2 (en) | 2016-11-18 | 2020-01-28 | Diehl Aviation Gilching Gmbh | Oxygen generator using ionic liquids |
| US10544511B2 (en) | 2016-11-18 | 2020-01-28 | Diehl Aviation Gilching Gmbh | Device for generating oxygen |
| US10549993B2 (en) | 2016-11-18 | 2020-02-04 | Diehl Aviation Gilching Gmbh | Method for generating oxygen from compositions comprising ionic liquids |
| US10589995B2 (en) | 2016-11-18 | 2020-03-17 | Diehl Aviation Gilching Gmbh | Methods using ionic liquids for decomposing peroxides |
| US10800656B2 (en) | 2016-11-18 | 2020-10-13 | Diehl Aviation Gilching Gmbh | Compositions comprising ionic liquids for decomposing peroxides |
| CN108069394B (en) * | 2016-11-18 | 2022-10-18 | 迪尔航空吉尔兴有限责任公司 | Method for generating oxygen from a composition comprising an ionic liquid |
| CN108069396B (en) * | 2016-11-18 | 2022-11-04 | 迪尔航空吉尔兴有限责任公司 | Composition comprising an ionic liquid for decomposing peroxides |
| CN108069395B (en) * | 2016-11-18 | 2022-11-15 | 迪尔航空吉尔兴有限责任公司 | Use of ionic liquids in compositions for generating oxygen |
| CN108069399B (en) * | 2016-11-18 | 2023-01-24 | 迪尔航空吉尔兴有限责任公司 | Oxygen generator for using ionic liquid |
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