CN104242031A - Singlet oxygen generator - Google Patents

Abstract

The invention provides a singlet oxygen generator. A cavity of the singlet oxygen generator is full of circulating-movement fillers with a large number of gaps, and the fillers perform circulating movement in the cavity; when moving to pass through the area between a reaction fluid inlet and a reaction fluid outlet in the lower portion of the cavity, the fillers are soaked with reaction fluid, fluid film is formed on the surfaces of the gaps of the fillers and then brought by the fillers into the area between a gas inlet and a gas outlet in the upper portion of the cavity for being reacted with gas entering the cavity, the reacted fluid film is taken away by the fillers from the upper portion of the cavity to return to the lower portion of the cavity for being updated, and gas generated by the reaction leaves the upper portion of the cavity and flows out from the gas outlet. The cavity of the singlet oxygen generator is fixed to a support outside the cavity, the fillers are driven in the mode that blades on a rotating shaft are driven by the rotating shaft, and the rotating shaft is driven by a certain rotating mechanical device through transmission connection.

Description

A singlet oxygen generator

technical field

The invention relates to a singlet oxygen generator applicable to a chemical oxygen iodine laser (hereinafter referred to as COIL), belonging to the field of high-energy chemical lasers.

Background technique

Due to the advantages of short wavelength, high power, ease of engineering amplification and good atmospheric transmission, COIL has broad potential application prospects, and has always attracted great attention from industrially developed countries. COIL is realized based on the near-resonance energy transfer process between singlet oxygen (the spectral symbol is O ₂ (a ¹ Δ _g ), hereinafter abbreviated as O ₂ ( ¹ Δ)) and I atoms:

$\mathrm{<span\; class="notranslate">\; I</span>}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; P</span>}_{\mathrm{<span\; class="notranslate">\; 3</span>}<span\; class="notranslate">\; /</span>\mathrm{<span\; class="notranslate">\; 2</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; \&Delta;</span>}_{\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; \&LeftRightArrow;</span>\mathrm{<span\; class="notranslate">\; I</span>}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; P</span>}_{\mathrm{<span\; class="notranslate">\; 1</span>}<span\; class="notranslate">\; /</span>\mathrm{<span\; class="notranslate">\; 2</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; o</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; x</span>}<span\; class="notranslate">\; )</span>$

I( ² P _1/2 )+hv→I( ² P _3/2 )+2hv λ=1.315μm

As the direct energy source of COIL, O ₂ ( ¹ Δ) is produced by the reaction of Cl ₂ gas and alkaline hydrogen peroxide (hereinafter referred to as BHP) solution in a singlet oxygen generator (hereinafter referred to as SOG):

Cl ₂ +H ₂ O ₂ +2KOH→O ₂ ( ¹ Δ)↑+2KCl+2H ₂ O

Therefore, the development of high-performance SOG is a key way to improve the performance of COIL.

The first SOG used in COIL is the bubbling SOG, which produces O ₂ ( ¹ Δ) by directly bubbling Cl ₂ bubbles into the BHP solution. The reaction efficiency is low, and the total reaction pressure is usually only about several hundred Pa, O ₂ ( ¹ Δ) partial pressure is even lower, and can only be used in subsonic COIL with low energy and low power. At present, the mainstream development direction of COIL is high-energy and high-power supersonic COIL, which puts forward higher requirements for SOG.

So far, there are mainly four types of SOGs with mature technology and which can be applied to supersonic COIL: (1) Rotary plate SOG. It rotates a group of circular plates partially immersed in BHP, forming a fresh BHP film on the surface of the upper half of the circular plate, when Cl ₂ passes through the gap between the circular plates, it reacts with the BHP film to generate O ₂ ( ¹ Δ), its typical working performance is reported by Kendrick et al. [IEEE Journal of QuantumElectronics, 1999, 35(12), pp.1759-1764]: when the Cl ₂ /He molar flow ratio is 1/3 and the total pressure is Under the condition of 6.5kPa, the yield of O ₂ ( ¹ Δ) is about 52%, and the partial pressure of O ₂ ( ¹ Δ) is about 800Pa. (2) Jet SOG. The BHP reacts with the _Cl2 gas flow by forming multiple continuous jets through a set of orifices drilled in the plate. Its typical working performance is reported by Hurlock et al. [Proceedings of SPIE, 2002, 4631, pp.101-115]: under the condition of no diluent gas and 2.7kPa pressure, the O ₂ ( ¹ Δ) yield is -65 %, Chlorine utilization rate -90%, O ₂ ( ¹ Δ) partial pressure -1.6kPa. Better working performance can also be obtained under very harsh conditions. For example, Zagidullin et al. [Quantum Electronics, 1994, 24 (2), pp.120-123] have reported that when using pure Cl ₂ and a total pressure of -13.3kPa , the yield of O ₂ ( ¹ Δ) is greater than 60%, and the utilization rate of chlorine gas is greater than 80%, so it can be estimated that the partial pressure of O ₂ ( ¹ Δ) is as high as 6.4kPa. (3) Uniform droplet SOG. It is actually an improved type of jet SOG, which splits the jet into a series of droplets by adding perturbation to increase the reaction specific surface area (the surface area of Cl ₂ in contact with BHP in unit reaction volume), but compared with jet SOG, its The overall working performance has not been significantly improved, because the liquid droplets are more likely to be entrained by the airflow into the subsequent laser cavity than the jet flow, and the working stability is greatly reduced. (4) Spiral spray SOG. The core of the SOG is the sprayer. The sprayer is a circular tube with multiple rows of small holes drilled on the wall. The outer wall of the circular tube is fixed with multiple sets of helical blades in parallel, forming a spiral shape with the inner wall of the cylinder sleeved outside it. In the reaction zone, the circular tube rotates at a certain angular velocity, BHP is thrown out at high speed through the small hole of the circular tube to form a droplet jet, and reacts with the Cl ₂ entering from the bottom of the SOG, and the O ₂ ( ¹ Δ) airflow generated depends on the centrifugal force and Droplet separation. Using this SOG, in 2001, Vyskubenko et al. [AIAA2001-3009, 32nd Plasmadynamics and LasersConference, Anaheim, CA, June2001] obtained a yield of 50% on a spiral spray SOG with a partial pressure of O ₂ ( ¹ Δ) of 10kPa When used on a supersonic COIL, the O ₂ ( ¹ Δ) partial pressure before the nozzle also reached 3kPa, which they believed was the highest O ₂ ( ¹ Δ) partial pressure that could be achieved in front of the supersonic nozzle at that time .

The use of centrifugal force is a trend in the development of efficient SOGs in recent years. Centrifugal SOGs that have been studied so far include the following types. (1) The spiral spray type SOG mentioned above. (2) Centrifugal bubbling SOG, which uses a rotating cylinder to generate a centrifugal acceleration of several hundred times the acceleration of gravity (hereinafter marked as g, 1g=9.8m/s ² ), Cl ₂ passes through the small hole and the BHP attached to the inner wall The liquid film reacts, and the generated O ₂ ( ¹ Δ) bubbles are quickly separated from the BHP liquid film under the action of the huge buoyancy force generated by the centrifugal acceleration. Using this type of SOG, Zagidullin et al. [Applied Physics Letters, 2005, 86, 231102; Quantum Electronics, 2005, 35(10), pp.907-908] obtained under the experimental conditions of centrifugal accelerations of 136g and 400g respectively The laser outputs of 770W and 1264W were obtained, and the chemical efficiencies reached 25.6% and 24.6%, respectively. (3) Centrifugal jet SOG, its main feature is that a rotatable gas-liquid separator is placed in the reaction chamber, which is composed of a group of radially arranged blades. Through a specially designed nozzle, BHP and Cl ₂ are simultaneously sprayed into the reaction chamber to form an aerosol, and the rapidly rotating blades will combine the mist droplets with the O ₂ ( ¹ Δ) airflow during the flow of the aerosol from the center to the outside separate. The preliminary experimental research by Kodymová et al [Proceedings of SPIE,2006,6261,62611S] showed that when the product of chlorine utilization rate and O ₂ ( ¹ Δ) yield before gas-liquid separation is about 45%, O ₂ ( ¹ Δ) ) partial pressure can reach -5.3kPa. (4) The centrifugal flow SOG of Yang Heping [Japanese Journal of Applied Physics, 2008, 47(7), pp.5450-5456], which is based on the 2004 Emanuel [Proceedings of SPIE, 2004, 5448, pp.233-241 ] proposed a centrifugal SOG concept that has no rotating parts and only relies on rotating liquid flow: BHP is quickly sprayed onto an arc-shaped concave surface through a constricted slit nozzle to form a rotating liquid flow, while Cl ₂ passes through the porous nozzle downstream of the nozzle The sintered stainless steel enters the rotating liquid flow and mixes with BHP to react. The huge centrifugal force generated by the rotating liquid flow helps the O ₂ ( ¹ Δ) bubbles to break away from the BHP liquid layer quickly. Preliminary research results show that this centrifugal flow SOG can achieve an O ₂ ( ¹ Δ) yield of nearly 65% at the SOG outlet, an O ₂ ( ¹ Δ) partial pressure of about 4.1kPa, and a chlorine utilization rate of more than 96%. However, due to the fact that the components that generate centrifugal force are too complex and the gas-liquid separation effect and reaction efficiency are not as ideal as in theory, it is difficult for this type of SOG to enter mainstream applications for a while.

SOG performance is reflected in two aspects of work stability and reaction efficiency. Generally speaking, the performance of the existing SOG is not satisfactory, and it is still far from the current development needs of high-energy and high-power COIL. SOG with mature technology has good stability, but the reaction efficiency needs to be improved; SOG developed in recent years has high potential reaction efficiency, but the technology is immature and the stability is poor. Therefore, the development of high-performance SOGs with high working stability and high reaction efficiency is of great significance to the future development of COIL.

Contents of the invention

The present invention provides a SOG applicable to COIL.

A kind of SOG applicable to COIL, which has a closed cylindrical generator cavity, a rotating shaft is arranged along the central axis of the cavity, and the two ends of the rotating shaft are rotatably connected to the two bottom walls of the cavity , blades are arranged on the rotating shaft, and the cavity is filled with fillers. The central axis of the cavity is arranged along the horizontal direction.

In order to facilitate the entry and exit of reactants and products, a gas inlet and a gas outlet are provided on the side or bottom wall of the upper part of the chamber, and a reaction liquid inlet and a reaction liquid outlet are provided on the lower side or bottom wall of the chamber.

In order to support and fix the SOG, a support is provided outside the cavity, and the cavity is fixed on the support.

In order to enable the filler to circulate in the cavity, the blades are flat and fixed on the shaft along the axial direction of the shaft. The shaft is driven by a rotating mechanical device through a transmission connection. The shaft rotates along its axis, driving the blades to rotate and driving The filling circulates in the cavity.

In order not to affect the penetration of reactants inside the filler, more than two through holes are opened on the blade.

In order to make SOG have as large a reaction specific surface area as possible, the filler is made of fillers in the shape of particles, ribbons, rods and/or blocks, such as balls, stainless steel ribbons, round rods, Raschig rings, separator rings, cross Rings, Pall rings, Bell saddles (arc saddles), Interox saddles (moment saddles), etc. are filled in the cavity, and there are many gaps inside the filler.

The key of the present invention is that the generator cavity is covered with fillers that circulate and have a large number of gaps. During operation, there is a reaction liquid in the area between the reaction liquid inlet and the reaction liquid outlet in the lower part of the cavity, and the filler circulates in the cavity. Movement, when it moves through the lower part of the cavity, the reaction liquid infiltrates the filler and forms a liquid film on the surface of its void, and the liquid film is then brought into the upper part of the cavity by the filler to the area between the gas inlet and the gas outlet and the incoming gas The reaction occurs, and the reacted liquid film is taken away from the upper part of the cavity by the filler and returned to the lower part of the cavity for renewal, while the gas generated by the reaction leaves the upper part of the cavity and flows out from the gas outlet.

Depending on the actual working conditions and requirements, the gas inlet and gas outlet on the upper part of the chamber and the reaction liquid inlet and reaction liquid outlet on the lower part of the chamber can be switched. Correspondingly, the gas flow direction and the reaction liquid flow direction are the same as The moving direction of the filler can be reversed or the same. Figure 1 only shows one situation, that is, the moving direction of the filling is opposite to that of the gas and the reaction liquid.

The principle of the present invention: Existing experiments and theoretical analysis show that the key to high-performance SOG is to increase the specific surface area of gas-liquid reaction as much as possible on the basis of maintaining work stability to improve reaction efficiency. In order to enhance the working stability, the present invention adheres a layer of reaction liquid film to the void surface of the filler, and the adhered liquid film is not easily blown away by the air flow, and is constantly renewed by the circular movement of the filler in the reaction chamber. ; And the increase of the gas-liquid reaction specific surface area can be achieved by increasing the void ratio of the filler.

The advantages of the present invention are: 1. High working stability, the reaction liquid film adheres to the filler, is not easy to be blown away by the air flow, and can work under the condition of high-intensity gas flow.

2. The reaction efficiency is high. The voids inside the filler can form a large gas-liquid reaction specific surface area, so it can still have a high reaction efficiency under high-intensity gas flow conditions.

3. The continuous working time is long, and the filler circulates in the reactor cavity to continuously update the reaction liquid film, so that the gas-liquid reaction continues.

Description of drawings

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but these embodiments do not limit the present invention.

Fig. 1 is one of the structural schematic diagrams of the present invention (a cross-sectional view perpendicular to the rotating shaft 7).

Fig. 2 is the second structural schematic diagram of the present invention (a cross-sectional view along the rotating shaft 7 and perpendicular to the support 9).

Detailed ways

Example 1:

Please refer to Figure 1. The SOG is composed of a cavity 1 , a filler 2 , a gas inlet 3 , a gas outlet 4 , a reaction liquid inlet 5 , a reaction liquid outlet 6 , a rotating shaft 7 , blades 8 and a support 9 .

A kind of SOG applicable to COIL, which has a closed cylindrical generator cavity, a rotating shaft is arranged along the central axis of the cavity, and the two ends of the rotating shaft are rotatably connected to the two bottom walls of the cavity , blades are arranged on the rotating shaft, and the cavity is filled with fillers.

The central axis of the cavity is set along the horizontal direction, the upper side wall of the cavity is provided with a gas inlet and gas outlet, and the lower side wall of the cavity is provided with a reaction liquid inlet and a reaction liquid outlet.

In order to support and fix the SOG, a support is provided outside the cavity, and the cavity is fixed on the support.

In order to enable the filler to circulate in the cavity, the blades are flat and fixed on the shaft along the axial direction of the shaft. The shaft is driven by a rotating mechanical device through a transmission connection. The shaft rotates along its axis, driving the blades to rotate and driving The filling circulates in the cavity.

There is a BHP solution in the region between the reaction solution inlet 5 and the reaction solution outlet 6 at the lower part of the cavity 1, and the BHP solution is composed of a 50% hydrogen peroxide aqueous solution and a 50% potassium hydroxide aqueous solution by volume. 1:1 mixed preparation. Cl ₂ gas flows into the upper part of the cavity 1 from the gas inlet 3 to react with the BHP liquid film brought up by the filler 2, and the O ₂ ( ¹ Δ) gas flow generated by the reaction flows out from the gas outlet 4 . Filler 2 consists of spherical balls with a diameter of 3 mm. The rotating shaft 7 is fixedly connected with the blade 8, the diameter of the rotating shaft 7 is 10 mm, and the thickness of the blade 8 is 2 mm. The rotating shaft 7 drives the blade 8 to rotate at an angular velocity ω, driving the filler 2 to circulate in the cavity 1 . The moving direction of the filler 2 is opposite to both the gas flow direction and the reaction liquid moving direction. The inner diameter of the cavity 1 is 100mm, the length along the rotating shaft 7 is 20mm, ω=3.14rad/s, the Cl flow rate at the gas inlet 3 is 10mmol/s, and the total pressure obtained at the gas outlet 4 is greater _than 4.0kPa, O 2 ( 1 Δ) gas flow with Cl ₂ utilization greater ^than 85%, O ₂ ( ¹ Δ) partial pressure greater than 1.7kPa, and _{O 2} ( ¹ Δ) yield greater than 50%.

Example 2:

Please refer to Figure 2. Figure 2 is improved on the basis of Figure 1, both of which have the same basic structure, the difference is that the gas inlet 3 and the gas outlet 4 are moved from the position of the cylinder side of the cavity 1 in Figure 1 to the position of the cylinder bottom of the cavity 1 in Figure 2, therefore, The gas flow direction is perpendicular to the movement direction of the filler 2 . The flow rate of Cl ₂ at the gas inlet 3 is 8 mmol/s, the total pressure obtained at the gas outlet 4 is greater than 3.3kPa, the utilization rate of Cl ₂ is greater than 80%, the partial pressure of O ₂ ( ¹ Δ) is greater than 1.3kPa, and the O ₂ ( ¹ Δ ) O ₂ ( ¹ Δ) gas stream with a yield greater than 50%.

Example 3:

Please refer to Figure 1. This embodiment is basically the same as Embodiment 1, except that the filler 2 is made of stainless steel ribbons with a thickness of 36 microns and a width of 1.5 mm, which are filled in the cavity 1, and the specific surface area is greater than 10 cm ⁻¹ . The flow rate of Cl ₂ at the gas inlet 3 is 10mmol/s, the total pressure obtained at the gas outlet 4 is greater than 4.0kPa, the utilization rate of Cl ₂ is greater than 85%, the partial pressure of O ₂ ( ¹ Δ) is greater than 1.7kPa, and the partial pressure of O ₂ ( ¹ Δ ) O ₂ ( ¹ Δ) gas stream with a yield greater than 50%.

Example 4:

Please refer to Figure 2. This embodiment is basically the same as Embodiment 2, the difference is that the filler 2 is made of stainless steel ribbons with a thickness of 36 microns and a width of 1.5 mm that are filled in the cavity 1, and the specific surface area is greater than 10 cm ^-1 . The Cl ₂ flow rate at the gas inlet 3 is 8 mmol/s, the total pressure at the gas outlet 4 is greater than 3.3kPa, the Cl ₂ utilization rate is greater than 80%, the O ₂ ( ¹ Δ) partial pressure is greater than 1.3kPa, and the O ₂ ( ¹ Δ ) O ₂ ( ¹ Δ) gas stream with a yield greater than 50%.

Example 5:

Please refer to Figure 1. This embodiment is basically the same as Embodiment 1, the difference is that the filler 2 consists of round rods, Raschig rings, partition rings, cross rings, and Pall rings that are filled in the cavity 1 with a minimum size of 3 mm and a maximum size of 5 mm. , Bell saddle (arc saddle) and Interlocks saddle (moment saddle), the specific surface area is greater than 10cm ^-1 . The flow rate of Cl ₂ at the gas inlet 3 is 10mmol/s, the total pressure obtained at the gas outlet 4 is greater than 4.0kPa, the utilization rate of Cl ₂ is greater than 85%, the partial pressure of O ₂ ( ¹ Δ) is greater than 1.7kPa, and the partial pressure of O ₂ ( ¹ Δ ) O ₂ ( ¹ Δ) gas stream with a yield greater than 50%.

Embodiment 6:

Please refer to Figure 2. This embodiment is basically the same as Embodiment 2, the difference is that the filler 2 consists of round rods, Raschig rings, separator rings, cross rings, and Pall rings that are filled in the cavity 1 with a minimum size of 3 mm and a maximum size of 5 mm. , Bell saddle (arc saddle) and Interlocks saddle (moment saddle), the specific surface area is greater than 10cm ^-1 . The flow rate of Cl ₂ at the gas inlet 3 is 8 mmol/s, the total pressure obtained at the gas outlet 4 is greater than 3.3kPa, the utilization rate of Cl ₂ is greater than 80%, the partial pressure of O ₂ ( ¹ Δ) is greater than 1.3kPa, and the O ₂ ( ¹ Δ ) O ₂ ( ¹ Δ) gas stream with a yield greater than 50%.

Claims (10)

1. A singlet oxygen generator, characterized in that it has a closed cylindrical generator cavity (1), and a rotating shaft (7) is provided along the central axis of the cavity (1), and the rotating shaft (7) The two ends of the shaft are rotatably connected to the two bottom walls of the cavity (1), blades (8) are arranged on the rotating shaft (7), and the cavity (1) is filled with fillers (2). 2. The singlet oxygen generator according to claim 1, characterized in that: the central axis of the cavity (1) is set along the horizontal direction, and the upper side or bottom wall of the cavity (1) is provided with The gas inlet (3) and the gas outlet (4), the lower side or bottom wall are provided with the reaction liquid inlet (5) and the reaction liquid outlet (6); the cavity (1) is provided with a support (9), The cavity (1) is fixed on the support (9). 3. The singlet oxygen generator according to claim 1, characterized in that: the blade (8) is flat and fixed on the rotating shaft (7) along the axial direction of the rotating shaft (7). 4. The singlet oxygen generator according to claim 1 or 3, characterized in that: more than two through holes are opened on the blade (8). 5. The singlet oxygen generator according to claim 1, characterized in that: the rotating shaft (7) is driven by a rotating mechanical device through a transmission connection, and the rotating shaft (7) rotates along its axis to drive the blades (8) The rotation drives the filler (2) to circulate in the cavity (1). 6. The singlet oxygen generator according to claim 1, characterized in that: the filler (2) is filled with one or more of fillers in the shape of granular, ribbon, rod or block. The cavity (1) is formed, and there is a void inside the filler (2). 7. The singlet oxygen generator according to claim 1, characterized in that: the central axis of the cavity (1) is set along the horizontal direction; When working, there is a reaction liquid in the area between the reaction liquid inlet (5) and the reaction liquid outlet (6) at the lower part of the cavity (1), and the filling (2) circulates in the cavity (1) , when it moves through the lower part of the cavity (1), the reaction liquid infiltrates the filling (2) and forms a liquid film on the surface of its void, and the liquid film is then brought into the upper gas inlet of the cavity (1) by the filling (2) The area between (3) and the gas outlet (4) reacts with the incoming gas, and the reacted liquid film is taken away from the upper part of the cavity (1) by the filler (2) and returned to the lower part of the cavity (1) for renewal. The gas generated by the reaction leaves the upper part of the cavity (1) and flows out from the gas outlet (4). 8. The singlet oxygen generator according to claim 2 or 7, characterized in that: the gas inlet (3) and the gas outlet (4) in the upper part of the cavity (1) are connected to each other and the reaction liquid inlet (5) in the lower part ) and the reaction liquid outlet (6) can be switched according to the actual working conditions and requirements, correspondingly, the gas flow direction, the reaction liquid flow direction and the filler (2) movement direction can be reversed or the same. 9. According to the described singlet oxygen generator of claim 6, it is characterized in that: the filler is a ball, a stainless steel ribbon, a round bar, a Raschig ring, a partition ring, a cross ring, a Pall ring, a Bell saddle (arc Saddle), Interlocks saddle (moment saddle) and so on one or more. 10. The singlet oxygen generator according to claim 5, wherein said certain rotating mechanical device is an electric motor or an internal combustion engine.