CN105776144B - A kind of creating singlet oxygen production method based on two phase transfer systems - Google Patents
A kind of creating singlet oxygen production method based on two phase transfer systems Download PDFInfo
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- CN105776144B CN105776144B CN201410787667.0A CN201410787667A CN105776144B CN 105776144 B CN105776144 B CN 105776144B CN 201410787667 A CN201410787667 A CN 201410787667A CN 105776144 B CN105776144 B CN 105776144B
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Abstract
The present invention relates to the production method of creating singlet oxygen in COIL technical field.The alkali ionic liquid immiscible with water and aqueous hydrogen peroxide solution are mixed to form two phase transfer systems by this method, and using the ionic liquid body phase after transfer and chlorine reaction to produce creating singlet oxygen, realize isolating for water and creating singlet oxygen.This method helps to reduce quenching effect of the water to creating singlet oxygen, and reduces the water content in creating singlet oxygen.On the other hand, because alkali ionic liquid has enrichment to hydrogen peroxide, it is expected to so that COIL limits this bottleneck problem in the concentration of hydrogen peroxide faced during raw material regeneration and effectively solved under the conditions of conventional art.Therefore, the present invention is respectively provided with significance to improving COIL creating singlet oxygen yield, reducing creating singlet oxygen water content and solve its raw material regeneration issues.
Description
Technical field
It is specifically a kind of to be based on alkali the present invention relates to a kind of production method of creating singlet oxygen in COIL
The creating singlet oxygen production method of the property phase transfer system of ionic liquid-aqueous hydrogen peroxide solution two.
Background technology
COIL is the currently the only chemical laser for successfully operating at electron state transition, and wavelength is 1.315 μ
M, atmospheric window is placed exactly in, is had a good application prospect in many aspects, thus obtain extensive attention.
Creating singlet oxygen (O2(1Δ)) energy source as oxygen-iodine chemical laser, dissociation, pumping to iodine pass can etc. process
With directly affecting, its concentration determines the important technology index such as COIL chemical efficiency to a certain extent, very
To determine laser can normal table operation.Therefore, the acquisition of creating singlet oxygen is COIL research, designed
One of matter of utmost importance faced in journey.
Although the production method of creating singlet oxygen has a variety of at present, for example the solution-air of chlorine and alkaline hydrogen peroxide solution is anti-
The Photosensitive reaction method etc. of the gas-solid reaction method of Ying Fa, chlorine and solid peroxide or superoxides, fullerene, currently,
The main or gas-liquid reaction method of practicality is obtained.This, which is primarily due to gas-liquid reaction method, can stablize, be quick, in large quantities
The creating singlet oxygen of high absolute concentration is obtained, meets the demand of COIL.
However, traditional gas-liquid system there is also some it is obvious the shortcomings that, wherein most serious be exactly participate in reaction alkali
Property hydrogenperoxide steam generator can be by substantial amounts of water (H2O) bring into laser.These H2O is carried along into Oxygen Generator by BHP first
In, in BHP and chlorine (Cl2) between under the heat effect of reaction that occurs, be extremely easy to be transferred in the gas phase of Oxygen Generator, enter one
The follow-up oxygen iodine mixing section of COIL is brought into step, so as to result in water (H2O) generally depositing in the laser
.There are some researches show hydrone (H2O) a large amount of generally existings in the laser are to cause active matter in COIL
The key factor that kind is seriously quenched.Because H2The vibration level of H-OH keys and active specy in O molecules (including singlet state
Oxygen and active iodine atom) resonance pass can energy level approach, active specy is easy to energy reaching H2O and return to ground state, so as to cause
Active specy is seriously quenched.
In view of the above-mentioned problems, a kind of solution method is H will to be likely to occur in reaction system2O place is with heavy water (D2O) replace
Generation, i.e., BHP is replaced using so-called alkaline deuterium-peroxide (BDP) solution, this makes it possible to avoid H2O is to the sudden of active specy
The effect of going out.Because utilize D2O replaces H2O does not change the chemical reaction characteristic of water, but because D atomic mass is different from H, its
Middle D-OD vibration level and H2In O there is larger difference in the vibration level of H-OH and active specy, so as to avoid activity
Resonance between species and water, which passes, caused to be inactivated.Result of study confirms, in H2O in O2(1Δ) the survival life-span be 3.8 μ s,
And in D2This time is extended to 62 μ s (A.A Gorman, Singlet oxygen, in CRC Handbook of in O
Organic Photochemistry,Vol.II(J.C.Scaiano Ed.),CRC press,Boca Raton,FL,p.229-
247,1989), D2O steam is H to the quenching effect of active iodine species2O steam 1/50 (J.Chem.Phys.Vol.64,
No.4,p.1850,1976)。
However, the operating cost of COIL greatly improved in above-mentioned solution method.Heavy water is in nature
Abundance is relatively low, and its extraction cost is high, routinely supply channel, and 99.9D.% heavy water price reaches ten thousand yuan or so per kilograms,
This causes the operating cost of COIL to become to be difficult to receive.
If it is possible to find a kind of new reaction system, the high-efficient characteristic of gas-liquid reaction system can be kept, again
It is avoided that H2Harmful effects of the O to active specy in COIL, then a kind of preferably creating singlet oxygen of can yet be regarded as produce
System.
The content of the invention
The present invention is produced in the existing creating singlet oxygen of analysis on the basis of system and method, it is proposed that one kind is used to produce substance
Two phase transfer systems of state oxygen, and the creating singlet oxygen based on the system produce new method.Basic process is as follows：A) by alkalescence from
Sub- liquid R. [OH], aqueous hydrogen peroxide solution are placed in same raw material storage tanks, and wherein R represents the cation of alkali ionic liquid
Group；B) mix, now R. [OH] absorbs hydrogen peroxide from aqueous hydrogen peroxide solution phase, and hydrogen peroxide is anti-with R. [OH]
R. [O should be converted into2H], eventually form containing R. [O2H] the two-phase system that coexists of ionic liquid body phase and water-soluble liquid phase；C) by ion
Liquid phase extract into singlet oxygen generator with chlorine reaction, generator exports i.e. can obtain creating singlet oxygen, it is another by what is obtained
Outer two kinds of product hydrogen peroxides, R. [Cl] and the complete R. [O of unreacted2H] in the return to step a) raw material storage tanks, peroxide
Changing hydrogen will be automatically into aqueous hydrogen peroxide solution phase, and R. [Cl] and the complete R. [O of unreacted2H] ionic liquid body phase will be entered.
Continuously by ionic liquid body phase extract into singlet oxygen generator with chlorine reaction, with the carry out raw material storage of reaction
Deposit R. [O in the ionic liquid body phase in tank2H] concentration is gradually reduced.Up to R. [O in the ionic liquid body phase in raw material storage tanks2H]
Concentration drops to the process of stopping step c) after setting endpoint concentration；Two electronics hydrogen reduction are inserted in aqueous hydrogen peroxide solution phase
Negative electrode, insertion analysis chlorine anode in ionic liquid body phase, be powered electrolysis, and R. [Cl] is converted R. [OH] again, and chlorine is recyclable sharp again
With, and concentration of hydrogen peroxide is able to lifting recovery in water-soluble liquid phase；Can repeat step c) again process, list can be continuously available
Weight state oxygen.The alkali ionic liquid is ionic liquid not soluble in water, and the alkali ionic liquid can be water-soluble with hydrogen peroxide
Liquid forms two phase stratification, and R group is strong hydrophobic group in the alkali ionic liquid, and R is at least one substitution position by six carbon
Above alkyl or the imidazoles or pyridine anionic group of the substitution of three carbon above fluorinated alkyls.R.[O2H] endpoint concentration is 3~
Any specific concentration in 5mol/L sections.Aqueous hydrogen peroxide solution concentration is more than 1mol/L, further preferably greater than 3mol/L.
This method has advantages below：
(1) quenching of creating singlet oxygen in the liquid phase is alleviated, more wide loose constraint is provided for the design of Oxygen Generator
Condition.H-OH keys are not present in ionic liquid, and in theory, the creating singlet oxygen time-to-live therein will be significantly increased, and it reduce right
The requirement of Oxygen Generator.
(2) presence of steam in Oxygen Generator is reduced.Contain substantial amounts of water in traditional BHP, in BHP and chlorine reaction
When be inevitably brought into gas phase, be further entrained among laser subsequent sections, the operation to laser is made
Into serious harmful effect.New two-phase system, into the only R. [O of generator2H], in the absence of the interference of water.
(3) raw material service efficiency is high, R. [OH] and H2O2Binding ability is strong, to H2O2With enrichment so that peroxidating
Thing is concentrated, and under comparable sodium Sharp criteria, improves 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, main is exactly that peroxide concentrations are difficult to reach laser requirement.Under the conditions of this method, due to R.
[OH] and H2O2Binding ability is strong, reduces the requirement to hydrogen peroxide regeneration concentration, is expected to so that raw material regeneration techniques bottleneck quilt
Smoothly solve.
Brief description of the drawings
Fig. 1 is the flow and schematic diagram that two phase transfer systems produce creating singlet oxygen.
Embodiment：
Embodiment 1
By 1 kilogram of alkali ionic liquid C3F7ImCH3The aqueous hydrogen peroxide solution that [OH], 1 kilogram of concentration are 5mol/L is put
In raw material storage tanks and mix, now C3F7ImCH3[OH] absorbs hydrogen peroxide from aqueous hydrogen peroxide solution phase,
C3F7ImCH3[OH] and hydroperoxidation generation C3F7ImCH3.[O2H], eventually form containing C3F7ImCH3.[O2H] ionic liquid
The two-phase system that body phase mutually coexists with aqueous hydrogen peroxide solution；Ionic liquid body phase is extracted to Small Jet formula creating singlet oxygen and occurred
In device with chlorine reaction, generator exports i.e. can obtain creating singlet oxygen, by obtained other two kinds of product hydrogen peroxides,
C3F7ImCH3[Cl] and the complete C of unreacted3F7ImCH3.[O2H] return in raw material storage tanks, hydrogen peroxide will be automatically into
Aqueous hydrogen peroxide solution phase, and C3F7ImCH3[Cl] and the complete C of unreacted3F7ImCH3.[O2H] ionic liquid body phase will be entered；
Continuous use, until C in ionic liquid body phase3F7ImCH3.[O2H] concentration stops after dropping to 3.7mol/L；In aquae hydrogenii dioxidi
Graphite cathode in solution, insertion analysis chlorine DSA anodes in ionic liquid body phase, be powered electrolysis, C3F7ImCH3[Cl] is converted again
C3F7ImCH3.[O2H], the recyclable recycling of chlorine, and concentration of hydrogen peroxide is able to lifting recovery in aqueous hydrogen peroxide solution phase.
Claims (6)
1. in a kind of creating singlet oxygen production method based on two phase transfer systems, it is characterised in that process is as follows：
a）Alkali ionic liquid R. [OH], aqueous hydrogen peroxide solution are placed in same raw material storage tanks, wherein R represent alkalescence from
The cation group of sub- liquid；
b）Mix, now R. [OH] absorbs hydrogen peroxide from aqueous hydrogen peroxide solution phase, and hydrogen peroxide is anti-with R. [OH]
R. [O should be converted into2H], eventually form containing R. [O2H] the two-phase system that coexists of ionic liquid body phase and water-soluble liquid phase；
c）Ionic liquid body phase is extracted into singlet oxygen generator and can obtain singlet state with chlorine reaction, generator exports
Oxygen, by obtained other two kinds of product hydrogen peroxides, R. [Cl] and the complete R. [O of unreacted2H] return to step a）The raw material
In holding vessel, hydrogen peroxide will be automatically into aqueous hydrogen peroxide solution phase, and R. [Cl] and the complete R. [O of unreacted2H] it will enter
Enter ionic liquid body phase；Continuously by ionic liquid body phase extract into singlet oxygen generator with chlorine reaction, with the progress of reaction
R. [O in ionic liquid body phase in raw material storage tanks2H] concentration is gradually reduced.
2. the creating singlet oxygen production method based on two phase transfer systems according to claim 1, it is characterised in that：Until raw material
R. [O in ionic liquid body phase in holding vessel2H] concentration stops step c after dropping to setting endpoint concentration）Process；In peroxide
Change and two electronics oxygen reduction cathodes are inserted in aqueous solution of hydrogen phase, insertion analysis chlorine anode in ionic liquid body phase, be powered electrolysis, R. [Cl] quilt
Again R. [OH], the recyclable recycling of chlorine are converted, and concentration of hydrogen peroxide is able to lifting recovery in water-soluble liquid phase；Can be again
Repeat step c）Process, creating singlet oxygen can be continuously available.
3. the creating singlet oxygen production method based on two phase transfer systems according to claim 1, it is characterised in that：The alkalescence
Ionic liquid is ionic liquid not soluble in water, and the alkali ionic liquid can form two phase stratification with aqueous hydrogen peroxide solution,
R group is strong hydrophobic group in the alkali ionic liquid, R at least one substitution position by six carbon above alkyl or three carbon with
The imidazoles or pyridine anionic group of upper fluorinated alkyl substitution.
4. the creating singlet oxygen production method based on two phase transfer systems according to claim 2, it is characterised in that：R.[O2H] eventually
Point concentration is any specific concentration in 3 ~ 5 mol/L sections.
5. the creating singlet oxygen production method based on two phase transfer systems according to claim 1, it is characterised in that：Hydrogen peroxide
Concentration of aqueous solution is more than 1 mol/L.
6. the creating singlet oxygen production method based on two phase transfer systems according to claim 5, it is characterised in that：Hydrogen peroxide
Concentration of aqueous solution is more than 3 mol/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3323782B1 (en) * | 2016-11-18 | 2019-08-14 | Diehl Aviation Gilching GmbH | Oxygen generating compositions comprising ionic liquids |
| EP3323779B1 (en) | 2016-11-18 | 2020-06-03 | Diehl Aviation Gilching GmbH | Method for generating oxygen using ionic liquids for decomposing peroxides |
| EP3323471B1 (en) * | 2016-11-18 | 2020-05-13 | Diehl Aviation Gilching GmbH | Device for generating oxygen |
| EP3323783B1 (en) * | 2016-11-18 | 2019-07-17 | Diehl Aviation Gilching GmbH | Use of ionic liquids in compositions for generating oxygen |
| EP3323470B1 (en) * | 2016-11-18 | 2022-06-29 | Diehl Aviation Gilching GmbH | Oxygen generator using ionic liquids |
| EP3323780B1 (en) | 2016-11-18 | 2020-05-20 | Diehl Aviation Gilching GmbH | Compositions comprising ionic liquids and peroxides |
| EP3323781B1 (en) | 2016-11-18 | 2019-08-14 | Diehl Aviation Gilching GmbH | Method for generating oxygen from compositions comprising ionic liquids |
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| CN101043120A (en) * | 2006-03-24 | 2007-09-26 | 中国科学院大连化学物理研究所 | Method for confecting chemical fuel of oxygen-iodine chemical laser |
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| US7116696B2 (en) * | 2002-06-10 | 2006-10-03 | Ksy Corporation | Efficient method and apparatus for generating singlet delta oxygen at an elevated pressure |
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| CN101043120A (en) * | 2006-03-24 | 2007-09-26 | 中国科学院大连化学物理研究所 | Method for confecting chemical fuel of oxygen-iodine chemical laser |
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