Efficient method and apparatus for generating singlet delta oxygen at an elevated pressure
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
H01S-003/22
H01S-003/14
H01S-003/095
H01S-003/09
A62B-007/08
A62B-007/00
C01B-013/00
출원번호
US-0453148
(2003-06-03)
발명자
/ 주소
Emanuel,George
출원인 / 주소
KSY Corporation
대리인 / 주소
Storm LLP
인용정보
피인용 횟수 :
16인용 특허 :
47
초록▼
An improved singlet delta oxygen generator (SOG) and method of its use are disclosed. The improved SOG is compact and scalable, capable of operating in a zero-gravity or low gravity environment, requires no gaseous diluent or buffer gas, and is capable of operating at pressures as high as one atmosp
An improved singlet delta oxygen generator (SOG) and method of its use are disclosed. The improved SOG is compact and scalable, capable of operating in a zero-gravity or low gravity environment, requires no gaseous diluent or buffer gas, and is capable of operating at pressures as high as one atmosphere. The improved SOG also efficiently utilizes the reactants and produces a O2(1Δ) stream that is largely free of chlorine and water vapor contamination and therefore does not require a BHP regeneration system or a water vapor trap. When used as part of a COIL system, the SOG may be part of a plenum that directly feeds the laser's nozzle. The close proximity of the SOG to the laser cavity allows operation of the SOG at higher pressures without significant depletion of available O2(1Δ) through collisional deactivation.
대표청구항▼
The invention claimed is: 1. A singlet delta oxygen generator capable of operating in low gravity comprising: an inlet for an aqueous basic hydrogen peroxide solution; a porous wall inlet for chlorine; a concave wall over which the basic hydrogen peroxide solution and chlorine flow and react to pr
The invention claimed is: 1. A singlet delta oxygen generator capable of operating in low gravity comprising: an inlet for an aqueous basic hydrogen peroxide solution; a porous wall inlet for chlorine; a concave wall over which the basic hydrogen peroxide solution and chlorine flow and react to produce singlet delta oxygen, byproducts, and a spent reactant solution. 2. A singlet delta oxygen generator according to claim 1 wherein the pressure in the generator is greater than 100 Torr. 3. A singlet delta oxygen generator according to claim 2 wherein the pressure in the generator is between about 100 Torr to about 760 Torr. 4. A singlet delta oxygen generator according to claim 1 further comprising a cooling system for cooling the basic hydrogen peroxide solution to a temperature not more than about 10째 C. above its freezing point prior to the inlet. 5. A singlet delta oxygen generator according to claim 4 wherein the basic hydrogen peroxide solution is cooled to a temperature not more than about 5째 C. above its freezing point prior to the inlet. 6. A singlet delta oxygen generator according to claim 4 wherein the basic hydrogen peroxide solution is diluted with water prior to the basic hydrogen peroxide inlet. 7. A singlet delta oxygen generator according to claim 6 wherein the dilute basic hydrogen peroxide solution comprises water, aqueous H2O2, and aqueous hydroxide solution, wherein the ratio of water to hydroxide is about 10 to 50 moles of water for every mole of hydroxide and wherein the ratio of H2O2 to hydroxide is about 0.5 to 1.10 moles of H2O2 for every mole of hydroxide. 8. A singlet delta oxygen generator according to claim 7 wherein the ratio of water includes any aqueous portion of the hydroxide solution and aqueous portion of the H2O2. 9. A singlet delta oxygen generator according to claim 1 wherein water vapor is a byproduct generated when the basic hydrogen peroxide and chlorine react and the amount of water vapor byproduct generated is reduced by cooling the basic hydrogen peroxide solution to a temperature not more than 10째 C. above its freezing point. 10. A singlet delta oxygen generator according to claim 9 without a water vapor trap. 11. A singlet delta oxygen generator according to claim 1 further comprising an outlet for the singlet delta oxygen and a separate outlet for the spent reactant solution. 12. A singlet delta oxygen generator according to claim 11 wherein the singlet delta oxygen outlet comprises an inlet to a nozzle feeding a laser cavity. 13. A singlet delta oxygen generator according to claim 12 wherein the pressure of the singlet delta oxygen at the inlet to the nozzle is the yield times the total pressure of about 100 to about 400 Torr. 14. A singlet delta oxygen generator according to claim 11 wherein the spent reactant solution is substantially disposed of through the spent reactant solution outlet. 15. A singlet delta oxygen generator according to claim 14 wherein regeneration of the solution for recycling to feed the basic hydrogen peroxide inlet is not performed. 16. A singlet delta oxygen generator according to claim 1 wherein no diluent gas is used. 17. A singlet delta oxygen generator according to claim 1 wherein the total pressure in the generator is between about 100 to about 400 Torn. 18. A singlet delta oxygen generator according to claim 1 wherein the basic. hydrogen peroxide solution comprises aqueous H 2O2 and an aqueous hydroxide solution wherein the molar flow rate of H2O2 is about 50-110% of the molar flow rate of the hydroxide solution. 19. A sinidet delta oxygen generator capable of operating in low gravity comprising: an inlet for an aqueous basic hydrogen peroxide solution, wherein the basic hydrogen peroxide solution comprises aqueous H2 O2 and an aqueous hydroxide solution, and wherein the molar flow rate of H2O2 is about 50-110% of the molar flow rate of the hydroxide solution; an inlet for chlorine; a concave wall over which the basic hydrogen en peroxide solution and chlorine flow and react to produce singlet delta oxygen, byproducts, and a spent reactant solution; and wherein the chlorine molar flow rate is about 80-95% of the molar flow rate of the hydroxide solution. 20. A singlet delta oxygen generator capable of operating in low gravity comprising an inlet for an aqueous basic hydrogen peroxide solution; a porous wall inlet for chlorine; a concave wall over which the basic hydrogen peroxide solution and chlorine flow and react to produce a singlet delta oxygen stream and a spent reactant solution; an outlet for the singlet delta oxygen stream wherein the singlet delta oxygen stream at the outlet comprises about 70% yield or greater singlet delta oxygen; wherein the pressure in the generator is between about 100 Torr to about 910 Torr. 21. A singlet delta oxygen generator comprising: an inlet for a basic hydrogen peroxide solution; an inlet porous wall nozzle to inject chlorine in a direction that is generally perpendicular to the direction of flow of the basic hydrogen peroxide solution; a concave wall along which the basic hydrogen peroxide solution and chlorine flow and react to produce singlet delta oxygen and a spent reactant solution; a nozzle for feeding the singlet delta oxygen to a laser cavity wherein the nozzle is located substantially opposite from the concave wall; and wherein the pressure in the generator is between about 100 Torr to about 760 Torr. 22. The singlet oxygen generator of claim 21 wherein a nozzle throat is located about 10 cm or less from the concave wall. 23. The singlet delta oxygen generator of claim 21 wherein the pressure in the generator is between about 100 Torr to about 400 Torr. 24. A method of producing singlet delta oxygen comprising: producing a dilute aqueous basic hydrogen peroxide solution comprising water, H2O2 and a hydroxide; cooling the aqueous basic hydrogen peroxide solution to a temperature not more than about 10째 C. above its freezing point; injecting the cooled aqueous basic hydrogen peroxide solution sufficient to create a high-speed fluid layer that flows along a concave wall in a singlet oxygen generator reactor, injecting chlorine into the reactor through a porous wall section to mix with the aqueous basic hydrogen peroxide solution; producing singlet delta oxygen vapor, byproducts, and spent aqueous reactant solution by reaction of the aqueous basic hydrogen peroxide solution and the chlorine; separating the singlet delta oxygen vapor from the aqueous solution by a pressure gradient associated with a centrifugal force; removing the singlet delta oxygen and gaseous byproducts from the reactor through an outlet; and removing the spent aqueous solution through a separate outlet. 25. The method of claim 24 wherein the singlet delta oxygen outlet comprises a plenum that directly feeds an inlet to a nozzle of a laser. 26. The method of claim 24 wherein the fluid layer has a thickness of about 15 mm or less. 27. The method of claim 26 wherein the fluid layer comprises a liquid layer and a frothy layer and wherein the liquid layer has a thickness of about 4 mm or less. 28. A method of producing singlet delta oxygen comprising: producing a dilute aqueous basic hydrogen peroxide solution comprising water, H2O2 and a hydroxide; cooling the aqueous basic hydrogen peroxide solution to a temperature not more than about 10째 C. above its freezing point; injecting the cooled aqueous basic hydrogen peroxide solution sufficient to create a high-speed fluid layer that flows along a concave wall in a singlet oxygen generator reactor, injecting chlorine into the reactor through the concave wall to mix with the aqueous basic hydrogen peroxide solution; producing singlet delta oxygen vapor, byproducts, and spent aqueous reactant solution by reaction of the aqueous basic hydrogen peroxide solution and the chlorine; separating the singlet delta oxygen vapor from the aqueous solution by a pressure gradient associated with a centrifugal force; removing the singlet delta oxygen and gaseous byproducts from the reactor through an outlet, wherein water vapor is one of the byproducts, and wherein the step of removing the singlet delta oxygen does not include passing the singlet delta oxygen through a water vapor trap; and removing the spent aqueous solution through a separate outlet. 29. The method of claim 24 wherein between the injecting step and removing step the aqueous solution remains in the reactor for less than about 20 milliseconds. 30. The method of claim 29 wherein the aqueous solution remains in the reactor for less than about 10 milliseconds. 31. The method of claim 24 wherein the reactor pressure is between about 100 Torr and 910 Torr. 32. The method of claim 25 wherein the pressure of the singlet delta oxygen at the nozzle inlet is between about 100 Torr to about 400 Torr. 33. The method of claim 24 wherein the basic hydrogen peroxide is injected through a converging nozzle. 34. The method of claim 24 further comprising cooling the H2O2 and hydroxide to temperatures not more than about 10째 C. above their freezing points. 35. A method of producing singlet delta oxygen comprising: producing a dilute aqueous basic hydrogen peroxide solution comprising water, H2O2 and a hydroxide wherein the H 2O2 has a molar flow rate that is about 50% to 110% of the hydroxide molar flow rate; cooling the aqueous basic hydrogen peroxide solution to a temperature not more than about 10째 C. above its freezing point; injecting the cooled a aqueous basic hydrogen peroxide solution sufficient to create a high-speed fluid layer that flows along a concave wall in a singlet oxygen generator reactor; injecting chlorine into the reactor through the concave wall to mix with the aqueous basic hydrogen peroxide solution, wherein the chlorine is injected into the reactor with a molar flow rate between about 80% to about 95% of the hydroxide molar flow rate; producing singlet delta oxygen vapor, byproducts, and spent aqueous reactant solution by reaction of the aqueous basic hydrogen peroxide solution and the chlorine; separating the singlet delta oxygen vapor from the aqueous solution by a pressure gradient associated with a centrifugal force; removing the singlet delta oxygen and gaseous byproducts from the reactor through an outlet; and removing the spent aqueous solution through a separate outlet. 36. The method of claim 24 wherein no basic hydrogen peroxide regeneration or recycling is performed. 37. The method of claim 24 wherein the dilute aqueous basic hydrogen peroxide solution comprises substantially non-recycled H 2O2 and hydroxide. 38. The method of claim 24 further comprising recycling the spent aqueous solution after the removing step and wherein less than 10% of the aqueous basic hydrogen peroxide in the injecting step comprises the recycled spent solution. 39. The method of claim 24 further comprising disposing of the spent aqueous solution removed through the separate outlet. 40. A singlet delta oxygen generator comprising an inlet for an aqueous basic hydrogen peroxide solution; a porous wall inlet for chlorine; a concave wall over which the basic hydrogen peroxide solution and chlorine flow and react to produce a singlet delta oxygen stream and a spent reactant solution; an exhaust duct for the singlet delta oxygen stream; wherein the pressure in the generator is between about 100 Torr to about 910 Torr. 41. A singlet delta oxygen generator according to claim 40 wherein the singlet delta oxygen stream exhaust duct comprises an inlet for a nozzle for a laser cavity. 42. A singlet delta oxygen generator according to claim 41 wherein the singlet delta oxygen stream at the nozzle inlet comprises about 70% or greater singlet delta oxygen yield. 43. A singlet delta oxygen generator according to claim 41 wherein the singlet delta oxygen stream at the nozzle inlet comprises about 85% or greater singlet delta oxygen yield. 44. A singlet delta oxygen generator according to claim 41 wherein no diluent gas is required. 45. A singlet delta oxygen generator according to claim 40 wherein the inlet for the basic hydrogen peroxide is a converging nozzle. 46. A singlet delta oxygen generator according to claim 41 wherein the total pressure at the inlet for the nozzle is about 100 Torr to about 400 Torr. 47. A singlet delta oxygen generator according to claim 41 wherein the singlet delta oxygen stream contains less than about 15% water vapor at the nozzle inlet without having passed the stream through a water vapor trap. 48. A method for producing singlet delta oxygen comprising: mixing water, precooled H2O2 and a precooled hydroxide solution to form a dilute aqueous basic hydrogen peroxide solution, wherein the H2O2 and hydroxide solution are precooled to temperatures not more than about 10째 C. above their freezing points; and cooling the dilute aqueous basic hydrogen peroxide solution to a temperature not more than about 10째 C. above its freezing point; injecting the dilute basic hydrogen peroxide solution into a reactor to create a fluid layer along a concave surface in the reactor wherein the thickness of the fluid layer is about 15 mm or less; injecting chlorine into the reactor tbrough a porous wall section; passing the basic hydrogen peroxide and chlorine solution through the reactor without the water vapor partial pressure reaching equilibrium; and reacting the basic hydrogen peroxide with the chlorine to produce singlet delta oxygen, salt byproduct, and water vapor byproduct. 49. The method according to claim 48 wherein the dilute basic hydrogen peroxide solution comprises water, H2O2, and a hydroxide solution in a molar ratio of about 10 or greater to 1 to 1, and wherein the ratio quantity of water comprises the water and any aqueous portion of the H2O2 and hydroxide solution. 50. The method of claim 48 wherein the basic hydrogen peroxide and chlorine pass through the reactor in less than about 20 milliseconds. 51. A singlet delta oxygen generator comprising a means for injecting a basic hydrogen peroxide solution into the generator to form a thin layer of solution along a concave surface of the generator; a means for injecting chlorine through a porous wall section into the generator to react with the basic hydrogen peroxide solution to form a singlet delta oxygen stream, water vapor, byproducts and contaminants without separating the solution from the concave surface of the generator; a means for providing the singlet delta oxygen stream to an inlet for a nozzle feeding a laser cavity wherein the singlet delta oxygen stream comprises less than about 15% water vapor with or without passing through a water vapor trap. 52. A singlet delta oxygen generator according to claim 51 wherein the singlet delta oxygen stream comprises less than about 10% water vapor with or without passing through a water vapor trap. 53. A singlet delta oxygen generator according to claim 52 further comprising a means for removing water vapor from the singlet delta oxygen stream. 54. A singlet delta oxygen generator according to claim 51 wherein the singlet delta oxygen stream at the nozzle inlet comprises about 30% or less byproducts and contaminants. 55. A method for injecting chlorine vapor into a singlet delta oxygen generator comprising: providing a high speed flow of an aqueous basic hydrogen peroxide solution to the generator; injecting chlorine vapor into the high speed flow of the aqueous basic hydrogen peroxide solution through a porous wall comprising pores with an average diameter of less than about 100 micron; and wherein the chlorine vapor bubbles are distorted through shear forces associated with the high speed aqueous basic hydrogen peroxide flow to provide greater contact surface for reaction between the chlorine vapor and the aqueous basic hydrogen peroxide solution.
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