CN113460966A - Ozone separation system and method for generating high-concentration ozone mixed gas by using liquid oxygen - Google Patents
Ozone separation system and method for generating high-concentration ozone mixed gas by using liquid oxygen Download PDFInfo
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- CN113460966A CN113460966A CN202110749063.7A CN202110749063A CN113460966A CN 113460966 A CN113460966 A CN 113460966A CN 202110749063 A CN202110749063 A CN 202110749063A CN 113460966 A CN113460966 A CN 113460966A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 243
- 239000007789 gas Substances 0.000 title claims abstract description 116
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000926 separation method Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 138
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 138
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 134
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 18
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/10—Preparation of ozone
- C01B13/11—Preparation of ozone by electric discharge
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
The invention discloses an ozone separation system and method for generating high-concentration ozone mixed gas by using liquid oxygen, and belongs to the technical field of ozone preparation. The oxygen-rich air conditioner comprises a first heat exchange tube, a heating device, an ozone generator, a second heat exchange tube, a third heat exchange tube, a fourth heat exchange tube and an air outlet in sequence in the oxygen flowing direction; the third heat exchange tube can exchange heat with the first heat exchange tube; the first heat exchange tube comprises a first input end and a first output end, liquid oxygen can be input into the first input end, and oxygen can be output from the first output end through heat exchange of the liquid oxygen; the third heat exchange tube comprises an oxygen output end and an ozone output end, and the ozone and oxygen mixed gas generated by the ozone generator can be respectively output from the ozone output end and the oxygen output end through heat exchange; the fourth heat exchange tube can exchange heat with the second heat exchange tube. The invention can effectively utilize the cold energy of the liquid oxygen and the oxygen generated by the liquid oxygen, thereby generating the ozone-oxygen mixed gas with high ozone concentration for direct use by users.
Description
Technical Field
The invention belongs to the technical field of ozone preparation, and particularly relates to an ozone separation system and method for generating high-concentration ozone mixed gas by using liquid oxygen.
Background
At present, ozone is widely applied to a plurality of fields such as sewage treatment, drinking water treatment and disinfection, food processing and sterilization and purification, perishable food storage, mildew prevention and preservation, medical sanitation, household disinfection and purification, chemical engineering and the like. The ozone is mainly prepared by high-voltage corona discharge in the preparation of ozone, but the concentration of the prepared ozone is very low due to the technical conditions. The ozone content is only about 10 vol% when oxygen is used as a raw material, and the ozone content is lower when air is used as a raw material gas. In order to ensure the concentration and the use efficiency of ozone, most of the prior industrial applications still use liquid oxygen as raw material gas to generate ozone after temperature rise and pressure reduction. Only 10% of raw material gas oxygen in the product is utilized to generate ozone, and the rest oxygen is discharged without being recycled, so that a large amount of oxygen is wasted, and the operation cost is high.
With the increasing year by year of the application of the ozone advanced oxidation technology, the ozone advanced oxidation technology and the use of the ozone generator are gradually accepted by the market and the owners, and the ozone concentration taken out by the ozone generator is low, the problem of low oxygen utilization rate leads the cost of the ozone advanced oxidation technology to be obviously increased, and the application range is limited. In order to increase the concentration of ozone at the ozone-utilizing end, researchers have sought to separate ozone from oxygen in order to achieve this goal. If ozone and oxygen can be separated, the concentration of ozone can be improved, oxygen can be recovered, the popularization and the use of ozone advanced oxidation technology are more facilitated, the utilization efficiency of ozone is improved, oxygen can be saved, and the operating cost is reduced.
Through retrieval, the chinese invention patent CN103663384A discloses a method for separating a mixed gas of oxygen and ozone and an ozone generating system using the same, which utilizes a heat exchanger and a cold medium to reduce the temperature of the mixed gas of ozone and oxygen to be between the boiling point temperature of ozone and the boiling point temperature of oxygen, so that ozone is converted into a liquid state, and oxygen is still in a gaseous state, thereby separating the mixed gas of oxygen and ozone; the invention also discloses an ozone generating system using the separation method, and the ozone generating system comprises an ozone generator, an air source of the ozone generator, an air source supply device of the ozone generator, a cold medium supply device, a heat exchanger and the like. Although the patent can effectively separate ozone and oxygen, a cold medium and a cold medium supply device are still inevitably used in the system, liquid ozone is separated and then gasified through a vaporizer, and meanwhile, a cold source required by separation and a heat source required by gasification are wasted; in addition, in the art, since the preparation of ozone with high purity is explosive and thus may not be used directly, even after the preparation of pure ozone, it is necessary to add a mixed gas such as oxygen and air to be mixed with ozone, and in this patent, extra air is added to be used as the mixed gas, which is a waste of a part of raw materials and processes.
Also, for example, the chinese invention patent CN112408334A discloses an ozone production system for increasing ozone yield and a method for producing ozone, which specifically discloses an air pretreatment device, an oxygen supply device and an ozone generator; the air pretreatment device is sequentially provided with an air compressor, an oil-water separator, a cold dryer, a suction dryer, an air filter and a pressure reducing valve; the oxygen supply device comprises a liquid oxygen vaporizer, gasified oxygen is merged into a gas transmission pipeline after a pressure reducing valve, and the gasified oxygen is mixed with air and then enters an ozone generator; the ozone generator comprises a plurality of reaction chambers, wherein a high-voltage electrode plate, a low-voltage electrode plate and a cooling water pipe are arranged in each reaction chamber, and mixed gas of oxygen and air is introduced into each reaction chamber in a parallel connection mode. The patent mainly improves the ozone generator, has advantages in the aspects of full reaction of raw materials and heat dissipation, and thus improves the yield of ozone, but the patent directly adopts the liquid oxygen gasifier to gasify liquid oxygen on the premise of using liquid oxygen, and the cold energy of the liquid oxygen is lost; in addition, the patent gives off the ozone which is finally separated out directly, and does not make any description on the subsequent operation, so that additional gas may be required to be added and mixed with the ozone.
In summary, although the ozone concentration produced by the ozone generator in the prior art is low, the technology for separating ozone and oxygen is basically mature; it is only under the condition of using liquid oxygen as raw material that it can effectively utilize the cold energy of liquid oxygen to separate ozone from oxygen and utilize the oxygen produced in gasification process, so that it is a current difficult problem to reduce energy consumption as far as possible.
Therefore, there is a need to design a device or method capable of effectively utilizing liquid oxygen to generate high-concentration ozone mixed gas, so as to recover oxygen and simultaneously increase the concentration of ozone, reduce the operation and investment cost, and meet the use requirements of people.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that in the prior art, when an ozone mixed gas is prepared by an ozone separation device or method based on low-temperature separation, an additional refrigerant medium and an additional gas are needed and the concentration of ozone is low, the invention provides an ozone separation system and method for generating a high-concentration ozone mixed gas by using liquid oxygen; through reasonably arranging the heat exchange tubes, the heating device, the ozone generator and the connection relationship among the heat exchange tubes, the heating device and the ozone generator, the problems that additional refrigerant medium and additional gas are needed and the concentration of ozone is low when the ozone mixed gas is prepared by the low-temperature separation-based ozone separation device or method are effectively solved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to an ozone separation system for generating high-concentration ozone mixed gas by using liquid oxygen, which sequentially comprises a first heat exchange tube, a heating device, an ozone generator, a second heat exchange tube, a third heat exchange tube, a fourth heat exchange tube and an air outlet in the flow direction of the oxygen; the third heat exchange tube can exchange heat with the first heat exchange tube; the first heat exchange tube comprises a first input end and a first output end, liquid oxygen can be input into the first input end, and oxygen can be output from the first output end through heat exchange of the liquid oxygen; the third heat exchange tube comprises an oxygen output end and an ozone output end, and the ozone and oxygen mixed gas generated by the ozone generator can be respectively output from the ozone output end and the oxygen output end through heat exchange; the fourth heat exchange tube can exchange heat with the second heat exchange tube; the fourth heat exchange tube comprises a fourth input end and a fourth output end, the fourth input end is connected with the oxygen output end of the third heat exchange tube, and the fourth output end and the ozone output end of the third heat exchange tube are both connected with the gas outlet.
Preferably, the heat exchanger further comprises a first heat exchanger, and the third heat exchange tube and the first heat exchange tube are both arranged in the first heat exchanger; the third heat exchange tube further comprises a third input end.
Preferably, the heat exchanger further comprises a second heat exchanger, and the fourth heat exchange tube and the second heat exchange tube are both arranged in the second heat exchanger; the second heat exchange tube also comprises a second input end and a second output end; the second output terminal is connected to the third input terminal.
Preferably, the heating device comprises a heating device input and a heating device output; the input end of the heating device is connected with the first output end, and the output end of the heating device is connected with the ozone generator.
Preferably, the heating device is an oxygen purifier; oxygen purifier includes heat exchange tube I, heater and heat exchange tube II in proper order on the oxygen flow direction, heat exchange tube I can carry out the heat transfer with heat exchange tube II.
Preferably, the ozone generator comprises a generator input and a generator output; the fan is arranged between the generator input end and the heating device output end and comprises a fan input end and a fan output end, the fan input end is connected with the heating device output end, and the fan output end is connected with the generator input end.
Preferably, the system further comprises a tail gas ozone destructor comprising a destructor input and a destructor output; the input end of the destroyer is connected with the fourth output end, and the output end of the destroyer is connected with the input end of the fan.
Preferably, the gas mixing tank is further included, the gas mixing tank comprises a mixing tank input end I and a mixing tank input end II, and the gas outlet is formed in the gas mixing tank; mixing tank input I links to each other with the fourth output, mixing tank input II links to each other with the ozone output.
Preferably, a first regulating valve is arranged on a pipeline connected between the input end I of the mixing tank and the fourth output end, and a second regulating valve is arranged on a pipeline connected between the input end II of the mixing tank and the ozone output end.
Preferably, the device also comprises a liquid oxygen tank, wherein a liquid oxygen output end is arranged on the liquid oxygen tank; the liquid oxygen output end is connected with the first input end.
The invention relates to an ozone separation method for generating high-concentration ozone mixed gas by using liquid oxygen, which is based on an ozone separation system for generating high-concentration ozone mixed gas by using liquid oxygen; and after the liquid oxygen is treated by the ozone separation system, mixed gas containing ozone and oxygen is generated.
Preferably, the specific operation steps are as follows:
(1) liquid oxygen is input into the first heat exchange tube through the first input end to exchange heat with the third heat exchange tube to generate oxygen;
(2) heating the oxygen generated in the step (1) to-10-20 ℃, and introducing into an ozone generator to generate a mixed gas A of ozone and oxygen;
(3) introducing the mixed gas A into a second heat exchange tube to exchange heat with a fourth heat exchange tube, and then introducing the mixed gas A into a third heat exchange tube to exchange heat with the first heat exchange tube to generate oxygen and liquid ozone N;
(4) introducing the oxygen generated in the step into a fourth heat exchange tube to exchange heat with the second heat exchange tube, and outputting to obtain oxygen M;
(5) mixing the oxygen M with the liquid ozone N, and outputting the mixture from the gas outlet to obtain a mixed gas B of ozone and oxygen.
Preferably, the fourth output end of the fourth heat exchange tube is connected with the input end of the generator of the ozone generator through a pipeline, a tail gas ozone destructor is arranged on the pipeline, and oxygen M output by the fourth output end is input into the ozone generator after being treated by the tail gas ozone destructor.
Preferably, the first line is through liquid oxygen, which has a temperature of about-180 ℃, a pressure of 0.8MPa and a flow rate of 3.5 kg/h; heat exchange power of the first heat exchanger0.24 kW; the second pipeline is used for passing oxygen, the temperature is-120 ℃, the pressure is 0.14MPa, and the flow is 3.5 kg/h; the third pipeline is used for passing oxygen, the temperature is-10 ℃, the pressure is 0.14MPa, the flow is 3.5kg/h, the pressure of the oxygen is increased by about 0.2MPa after the oxygen is pressurized by a fan with 0.25kW on the fourth pipeline, and the flow is 5m3H; the fifth pipeline passes through a mixed gas A of ozone and oxygen, the temperature of the mixed gas A is 20 ℃, the pressure is 0.2MPa, the flow of the oxygen is 9kg/h, and the flow of the ozone is 1 kg/h; the heat exchange power of the second heat exchanger is 0.4 kW; the sixth pipeline passes through a gas-liquid mixture of ozone and oxygen, the temperature is-110 ℃, the pressure is 0.2MPa, and the flow is 10 kg/h; the seventh pipeline is used for passing oxygen, the temperature is-170 ℃, the pressure is 0.2MPa, and the flow is 9 kg/h; the eighth pipeline passes through liquid ozone, the temperature is-170 ℃, the pressure is 0.2MPa, and the flow is 1 kg/h; the ninth pipeline is used for passing oxygen, the temperature is 0 ℃, the pressure is 0.2MPa, and the flow is 9 kg/h; the tenth pipeline passes through oxygen with the temperature of 0 ℃, the pressure of 0.14MPa and the flow of 2.5 kg/h; the eleventh line passes oxygen at a temperature of 0 deg.C, a pressure of 0.14MPa and a flow of 6.5 kg/h.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to an ozone separation system for generating high-concentration ozone mixed gas by using liquid oxygen, which sequentially comprises a first heat exchange tube, a heating device, an ozone generator, a second heat exchange tube, a third heat exchange tube, a fourth heat exchange tube and an air outlet in the flow direction of the oxygen; the third heat exchange tube can exchange heat with the first heat exchange tube; the first heat exchange tube comprises a first input end and a first output end, liquid oxygen can be input into the first input end, and oxygen can be output from the first output end through heat exchange of the liquid oxygen; the third heat exchange tube comprises an oxygen output end and an ozone output end, and the ozone and oxygen mixed gas generated by the ozone generator can be respectively output from the ozone output end and the oxygen output end through heat exchange; the fourth heat exchange tube can exchange heat with the second heat exchange tube; the fourth heat exchange tube comprises a fourth input end and a fourth output end, the fourth input end is connected with the oxygen output end of the third heat exchange tube, and the fourth output end and the ozone output end of the third heat exchange tube are both connected with the gas outlet; through the arrangement, firstly, the third heat exchange tube and the first heat exchange tube exchange heat, the ozone and oxygen mixed gas A generated by the ozone generator can be separated by utilizing the cold energy of liquid oxygen, so that extra cold medium is saved, secondly, the heating device provides heat for heat exchange between the heat exchange tubes for the whole system, on one hand, a basis for cooling and separating the ozone and oxygen mixed gas generated by the ozone generator is provided, on the other hand, output oxygen with higher temperature is obtained under the heat exchange action of the fourth heat exchange tube and the second heat exchange tube, at the moment, the output oxygen and the separated liquid ozone are mixed to obtain the mixed gas B, and the mixed gas B can be used without adding extra mixed gas or further gasifying the liquid ozone, so that the energy is effectively saved; in conclusion, under the treatment effect of the ozone separation system, the liquid oxygen can also serve as a refrigerant medium and a mixed gas source, and the cold energy and the generated oxygen can be effectively utilized, so that the ozone-oxygen mixed gas with high ozone concentration is generated for direct use by users.
(2) The ozone separation system for generating the high-concentration ozone mixed gas by using the liquid oxygen does not need to dismantle the original device for the existing ozone advanced oxidation project, and can effectively utilize the cold energy of the liquid oxygen and the oxygen generated by the liquid oxygen by only adding part of heat exchange pipelines and connecting pipelines between the heat exchange pipelines, thereby reducing the operation cost.
(3) The invention relates to an ozone separation method for generating high-concentration ozone mixed gas by using liquid oxygen, which is based on an ozone separation system for generating high-concentration ozone mixed gas by using liquid oxygen; treating the liquid oxygen by the ozone separation system to generate a mixed gas containing ozone and oxygen; by the method, liquid oxygen can be used as a reactant for generating ozone, can also serve as a refrigerant medium and can be used as a mixed gas source, on the basis, the proportion of ozone in the finally prepared ozone-oxygen mixed gas can be regulated and controlled within the range of 0 wt% -28.57 wt% when the mixed gas is used for rear-end sewage treatment, so that the concentration of ozone in the ozone-oxygen mixed gas can be regulated and controlled within the wide range to meet the use requirements of different occasions and different personnel, and the concentration of ozone can reach 28.57 wt% at most, which is far higher than that of a conventional ozone generator generating ozone with the concentration of about 10 wt%, and the problem that the concentration of ozone generated by the conventional ozone generator is low is solved.
Drawings
FIG. 1 is a schematic diagram I of an ozone separation system for generating a high concentration ozone mixed gas using liquid oxygen according to the present invention;
FIG. 2 is a schematic diagram II of an ozone separation system for generating a high concentration ozone mixed gas by using liquid oxygen according to the present invention.
In the figure:
100. a liquid oxygen tank; 101. a liquid oxygen output end;
200. a first heat exchanger; 210. a first heat exchange tube; 211. a first input terminal; 212. a first output terminal; 220. a third heat exchange tube; 221. a third input terminal; 222. an ozone output end; 223. an oxygen output end; 280. a second regulating valve;
300. a heating device; 310. a heat exchange tube I; 311. an input end of a heating device; 320. a heater; 330. a heat exchange pipe II; 331. an output end of the heating device;
400. a fan; 401. a fan input end; 402. a fan output end;
500. an ozone generator; 501. a generator input; 502. a generator output;
600. a second heat exchanger; 610. a second heat exchange tube; 611. a second output terminal; 612. a second input terminal; 620. a fourth heat exchange tube; 621. a fourth input terminal; 622. a fourth output terminal;
700. a tail gas ozone destructor; 701. a destructor input; 702. a destructor output; 780. a first regulating valve;
800. a gas mixing tank; 801. an input end I of the mixing tank; 802. an input end II of the mixing tank; 803. an air outlet;
901. a first pipeline; 902. a second pipeline; 903. a third pipeline; 904. a fourth pipeline; 905. a fifth pipeline; 906. a sixth pipeline; 907. a seventh pipeline; 908. an eighth pipeline; 909. a ninth conduit; 910. a tenth pipeline; 911. an eleventh line.
Detailed Description
The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
The structure, proportion, size and the like shown in the drawings are only used for matching with the content disclosed in the specification, so that the person skilled in the art can understand and read the description, and the description is not used for limiting the limit condition of the implementation of the invention, so the method has no technical essence, and any structural modification, proportion relation change or size adjustment still falls within the scope covered by the technical content disclosed by the invention without affecting the effect and the achievable purpose of the invention. Also, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention is further described with reference to specific examples.
Example 1
The embodiment provides an ozone separation system for generating high-concentration ozone mixed gas by using liquid oxygen, which sequentially comprises a liquid oxygen tank 100, a first heat exchange tube 210, a heating device 300, an ozone generator 500, a second heat exchange tube 610, a third heat exchange tube 220, a fourth heat exchange tube 620 and an air outlet 803 in the flow direction of oxygen; the liquid oxygen tank 100 is provided with a liquid oxygen output end 101, and the liquid oxygen output end 101 is connected with a first input end 211; the third heat exchange pipe 220 can exchange heat with the first heat exchange pipe 210; the first heat exchange tube 210 comprises a first input end 211 and a first output end 212, the first input end 211 can input liquid oxygen, and the liquid oxygen can output oxygen from the first output end 212 through heat exchange; the third heat exchange tube 220 comprises an oxygen output end 223 and an ozone output end 222, and the mixed gas of ozone and oxygen generated by the ozone generator 500 can be respectively output from the ozone output end 222 and the oxygen output end 223 through heat exchange; the fourth heat exchange pipe 620 can exchange heat with the second heat exchange pipe 610; the fourth heat exchange tube 620 comprises a fourth input end 621 and a fourth output end 622, the fourth input end 621 is connected with the oxygen output end 223 of the third heat exchange tube 220, and the fourth output end 622 and the ozone output end 222 of the third heat exchange tube 220 are both connected with the air outlet 803.
In the present embodiment, a first heat exchanger 200 and a second heat exchanger 600 are further included; the third heat exchange pipe 220 and the first heat exchange pipe 210 are both arranged in the first heat exchanger 200; the third heat exchange tube 220 further comprises a third input end 221; the fourth heat exchange tube 620 and the second heat exchange tube 610 are both arranged in the second heat exchanger 600; the second heat exchange tube 610 further comprises a second input end 612 and a second output end 611; the second output end 611 is connected to the third input end 221; therefore, in the embodiment, only two third heat exchange tubes 220 and a first heat exchange tube 210 which exchange heat with each other are arranged in the first heat exchanger 200, and two input ends and three output ends are arranged on the first heat exchanger 200, so that the heat exchange and separation operation of ozone can be completed, meanwhile, the heat exchange efficiency between the heat exchange tubes is effectively improved, and energy loss is avoided; the second heat exchanger 600 has the same principle, and the second heat exchanger 600 is provided with two fourth heat exchange tubes 620 and a second heat exchange tube 610 which exchange heat with each other, and the second heat exchanger 600 is provided with two input ends and two output ends to complete heat exchange operation.
In addition, the heating device 300 is an oxygen purifier, the oxygen purifier sequentially comprises a heat exchange tube I310, a heater 320 and a heat exchange tube II 330 in the oxygen flowing direction, and the heat exchange tube I310 can exchange heat with the heat exchange tube II 330; the heat exchange tube I310 is provided with a heating device input end 311, and the heat exchange tube II 330 is provided with a heating device output end 331; the input end 311 of the heating device is connected with the first output end 212, and the output end 331 of the heating device is connected with the ozone generator 500; therefore, when oxygen with the temperature of about-120 ℃ is treated by the oxygen purifier, the temperature of the oxygen can be firstly increased to about 700 ℃ to remove the combustible impurities, and then the temperature of the oxygen is reduced to about 0 ℃ through the heat exchange between the heat exchange pipe I310 and the heat exchange pipe II 330, so that the combustible impurities are removed while the temperature of the oxygen is moderately increased. The ozone generator 500 comprises a generator input 501 and a generator output 502; a fan 400 is arranged between the generator input end 501 and the heating device output end 331, the fan 400 comprises a fan input end 401 and a fan output end 402, the fan input end 401 is connected with the heating device output end 331, and the fan output end 402 is connected with the generator input end 501; the exhaust gas ozone destructor 700 is further included, the exhaust gas ozone destructor 700 including a destructor input 701 and a destructor output 702; the breaker input end 701 is connected with the fourth output end 622, and the breaker output end 702 is connected with the fan input end 401; therefore, not only the oxygen gas of about 0 ℃ obtained by the oxygen purifier treatment is introduced into the ozone generator 500 to react, but also the oxygen gas outputted from the fourth output port 622 is introduced into the ozone generator 500 to react, thereby further utilizing the oxygen gas oxidized from the liquid oxygen in the liquid oxygen tank 100.
The ozone separation system in this embodiment further includes a gas mixing tank 800, the gas mixing tank 800 includes a mixing tank input end i 801 and a mixing tank input end ii 802, and the gas outlet 803 is disposed on the gas mixing tank 800; the input end I801 of the mixing tank is connected with the fourth output end 622, and the input end II 802 of the mixing tank is connected with the ozone output end 222; a first regulating valve 780 is arranged on a pipeline connected between the input end I801 of the mixing tank and the fourth output end 622, and a second regulating valve 280 is arranged on a pipeline connected between the input end II 802 of the mixing tank and the ozone output end 222; the liquid ozone and the oxygen are mixed by the gas mixing tank 800, the liquid ozone and the oxygen can be fully subjected to heat exchange, so that the liquid ozone is gasified, and in addition, the ozone and oxygen mixed gas with required proportion can be obtained under the regulating action of the first regulating valve 780 and the second regulating valve 280, so that a user can directly use the ozone and the oxygen.
The present embodiment also provides an ozone generating method for generating a high concentration ozone mixed gas by using liquid oxygen, which is based on the ozone separation system for generating a high concentration ozone mixed gas by using liquid oxygen described in the present embodiment; the method comprises the following steps of (1) processing liquid oxygen by the ozone separation system to generate mixed gas containing ozone and oxygen, and specifically comprises the following operation steps:
(1) inputting liquid oxygen with the temperature of-180 ℃, the pressure of 0.8MPa and the flow of 3.5kg/h in the liquid oxygen tank 100 into a first heat exchanger 200 with the heat exchange power of 0.24kW through a first pipeline 901, and exchanging heat between the liquid oxygen and a third heat exchange tube 220 in a first heat exchange tube 210 of the first heat exchanger 200 to generate oxygen with the temperature of-120 ℃, the pressure of 0.14MPa and the flow of 3.5 kg/h;
(2) heating the oxygen generated in the step (1) to-10 ℃ by an oxygen purifier, introducing the oxygen into a fan 400 at a pressure of 0.14MPa and a flow rate of 3.5kg/h for pressurization, and pressurizing the oxygen by the fan 400 at a pressure of 0.2MPa and a flow rate of 5m3Introducing into an ozone generator 500 to react to generate a mixed gas A of ozone and oxygen, wherein the temperature of the oxygen in the mixed gas A is 20 ℃, the pressure is 0.2MPa, the flow is 9kg/h, the temperature of the ozone is 20 ℃, the pressure is 0.2MPa, and the flow is 1 kg/h;
(3) introducing the mixed gas A into a second heat exchange tube 610 and a fourth heat exchange tube 620 in a second heat exchanger 600 with the heat exchange power of 0.4kW to exchange heat to obtain a gas-liquid mixture of ozone and oxygen, wherein the temperature is-110 ℃, the pressure is 0.2MPa, and the flow is 10 kg/h; then, introducing the gas-liquid mixture into a third heat exchange tube 220 to exchange heat with the first heat exchange tube 210 to generate oxygen and liquid ozone N, wherein the temperature of the oxygen is-170 ℃, the pressure is 0.2MPa, and the flow is 9kg/h, and the temperature of the liquid ozone N is-170 ℃, the pressure is 0.2MPa, and the flow is 1 kg/h;
(4) introducing the oxygen generated in the step (3) into a fourth heat exchange tube 620 to exchange heat with a second heat exchange tube 610, and outputting to obtain oxygen M, wherein the temperature of the oxygen M is 0 ℃, the pressure is 0.2MPa, and the flow is 9 kg/h; oxygen M is split into two branches: introducing oxygen with the temperature of 0 ℃, the pressure of 0.14MPa and the flow of 2.5kg/h into the gas mixing tank 800 through a tenth pipeline 910; the other path of oxygen with the temperature of 0 ℃, the pressure of 0.14MPa and the flow rate of 6.5kg/h is introduced into the tail gas ozone destructor 700 from the eleventh pipeline 911 to remove possible residual ozone, and then enters the ozone generator 500 for recycling as supplementary raw material oxygen through the fan 400;
(5) introducing the oxygen M in the step (4) and the liquid ozone N in the step (3) into a gas mixing tank 800 for mixing, and outputting a mixed gas B of ozone and oxygen from a gas outlet 803 after mixing; the temperature of the mixed gas B and the ozone concentration thereof can be adjusted by controlling the first adjusting valve 780 and the second adjusting valve 280 to meet different requirements.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. When a "flow, pressure, temperature, concentration, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction. "
Claims (13)
1. An ozone separation system for generating high-concentration ozone mixed gas by using liquid oxygen is characterized by sequentially comprising a first heat exchange tube (210), a heating device (300), an ozone generator (500), a second heat exchange tube (610), a third heat exchange tube (220), a fourth heat exchange tube (620) and a gas outlet (803) in the flow direction of oxygen;
the third heat exchange pipe (220) can exchange heat with the first heat exchange pipe (210); the first heat exchange tube (210) comprises a first input end (211) and a first output end (212), liquid oxygen can be input into the first input end (211), and oxygen can be output from the first output end (212) through the liquid oxygen after heat exchange; the third heat exchange tube (220) comprises an oxygen output end (223) and an ozone output end (222), and the ozone and oxygen mixed gas generated by the ozone generator (500) can be respectively output from the ozone output end (222) and the oxygen output end (223) through heat exchange;
the fourth heat exchange pipe (620) can exchange heat with the second heat exchange pipe (610); the fourth heat exchange tube (620) comprises a fourth input end (621) and a fourth output end (622), the fourth input end (621) is connected with the oxygen output end (223) of the third heat exchange tube (220), and the fourth output end (622) and the ozone output end (222) of the third heat exchange tube (220) are connected with the air outlet (803).
2. The ozone separation system for generating the high-concentration ozone mixed gas by using the liquid oxygen as claimed in claim 1, further comprising a first heat exchanger (200), wherein the third heat exchange pipe (220) and the first heat exchange pipe (210) are both arranged in the first heat exchanger (200); the third heat exchange tube (220) further comprises a third input end (221).
3. The ozone separation system for generating the high-concentration ozone mixed gas by using the liquid oxygen as claimed in claim 2, further comprising a second heat exchanger (600), wherein the fourth heat exchange pipe (620) and the second heat exchange pipe (610) are both arranged in the second heat exchanger (600); the second heat exchange tube (610) further comprises a second input end (612) and a second output end (611); the second output terminal (611) is connected to the third input terminal (221).
4. The ozone separation system for generating a high concentration ozone mixed gas using liquid oxygen as claimed in claim 1, wherein the heating means (300) comprises a heating means input terminal (311) and a heating means output terminal (331); the input end (311) of the heating device is connected with the first output end (212), and the output end (331) of the heating device is connected with the ozone generator (500).
5. The ozone separation system for generating a high concentration ozone mixed gas using liquid oxygen as claimed in claim 4, wherein the heating means (300) is an oxygen purifier; oxygen purifier includes heat exchange tube I (310), heater (320) and heat exchange tube II (330) in proper order on the oxygen flow direction, heat exchange tube I (310) can carry out the heat transfer with heat exchange tube II (330).
6. The ozone separation system for generating a high concentration ozone mixed gas using liquid oxygen as claimed in claim 4, wherein said ozone generator (500) comprises a generator input terminal (501) and a generator output terminal (502); a fan (400) is arranged between the generator input end (501) and the heating device output end (331), the fan (400) comprises a fan input end (401) and a fan output end (402), the fan input end (401) is connected with the heating device output end (331), and the fan output end (402) is connected with the generator input end (501).
7. The ozone separation system for generating a high concentration ozone mixed gas by using liquid oxygen as claimed in claim 6, further comprising a tail gas ozone destructor (700), wherein the tail gas ozone destructor (700) comprises a destructor input terminal (701) and a destructor output terminal (702); the destroyer input end (701) is connected with the fourth output end (622), and the destroyer output end (702) is connected with the fan input end (401).
8. The ozone separation system for generating the high-concentration ozone mixed gas by using the liquid oxygen as claimed in claim 1, further comprising a gas mixing tank (800), wherein the gas mixing tank (800) comprises a mixing tank input end I (801) and a mixing tank input end II (802), and the gas outlet (803) is arranged on the gas mixing tank (800); the mixing tank input end I (801) is connected with the fourth output end (622), and the mixing tank input end II (802) is connected with the ozone output end (222).
9. The ozone separation system for generating the high concentration ozone mixed gas by using the liquid oxygen as claimed in claim 8, wherein a first regulating valve (780) is arranged on a pipeline connected between an input end I (801) and a fourth output end (622) of the mixing tank, and a second regulating valve (280) is arranged on a pipeline connected between an input end II (802) and an ozone output end (222) of the mixing tank.
10. The ozone separation system for generating the high-concentration ozone mixed gas by using the liquid oxygen as claimed in any one of claims 1 to 9, further comprising a liquid oxygen tank (100), wherein the liquid oxygen tank (100) is provided with a liquid oxygen output end (101); the liquid oxygen output end (101) is connected with the first input end (211).
11. An ozone separation method for generating a high concentration ozone mixed gas by using liquid oxygen, which is characterized in that the ozone separation system for generating a high concentration ozone mixed gas by using liquid oxygen according to any one of claims 1 to 10; and after the liquid oxygen is treated by the ozone separation system, mixed gas containing ozone and oxygen is generated.
12. The ozone separation method for generating a high-concentration ozone mixed gas by using liquid oxygen as claimed in claim 11, comprising the following steps:
(1) liquid oxygen is input into the first heat exchange tube (210) through the first input end (211) and exchanges heat with the third heat exchange tube (220) to generate oxygen;
(2) heating the oxygen generated in the step (1) to-10-20 ℃, and introducing into an ozone generator (500) to generate a mixed gas A of ozone and oxygen;
(3) introducing the mixed gas A into a second heat exchange tube (610) to exchange heat with a fourth heat exchange tube (620), and then introducing the mixed gas A into a third heat exchange tube (220) to exchange heat with a first heat exchange tube (210) to generate oxygen and liquid ozone N;
(4) introducing the oxygen generated in the step (3) into a fourth heat exchange tube (620) to exchange heat with a second heat exchange tube (610), and outputting to obtain oxygen M;
(5) mixing the oxygen M with the liquid ozone N, and outputting a mixed gas B of ozone and oxygen through an air outlet (803).
13. The ozone separation method for generating the ozone mixed gas with high concentration by using the liquid oxygen as claimed in claim 12, wherein a fourth output end (622) of the fourth heat exchange pipe (620) is connected with a generator input end (501) of the ozone generator (500) through a pipeline, a tail gas ozone destructor (700) is arranged on the pipeline, and the oxygen M output from the fourth output end (622) is processed by the tail gas ozone destructor (700) and then is input into the ozone generator (500).
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2864757A (en) * | 1956-02-17 | 1958-12-16 | Air Reduction | Ozone concentration and dilution |
| GB955825A (en) * | 1960-04-25 | 1964-04-22 | British Oxygen Co Ltd | Production of ozonised oxygen |
| EP0498585A2 (en) * | 1991-02-05 | 1992-08-12 | The BOC Group plc | Production of ozone |
| EP0560166A1 (en) * | 1992-03-10 | 1993-09-15 | Linde Aktiengesellschaft | Process and apparatus for the production of ozone |
| US5624734A (en) * | 1996-02-21 | 1997-04-29 | Rees; Darci L. | Continuous process and apparatus for generation of ozone for industrial application with cryogenic refrigeration |
| CN202864913U (en) * | 2012-09-14 | 2013-04-10 | 福建新大陆环保科技有限公司 | Ozone generation system capable of separating produced mixed gas |
| CN103663384A (en) * | 2012-09-14 | 2014-03-26 | 福建新大陆环保科技有限公司 | Method for separating mixed gas of oxygen and ozone and ozone generating system using method |
| EP3235786A1 (en) * | 2016-04-21 | 2017-10-25 | Messer Group GmbH | Device and method for generating ozone |
| CN109455672A (en) * | 2018-12-31 | 2019-03-12 | 北京清源中科环保科技有限公司 | The system and method for generating ozone and liquefaction separation using liquid oxygen |
| CN112408334A (en) * | 2020-12-02 | 2021-02-26 | 江西蓝星星火有机硅有限公司 | Ozone production system for improving ozone yield and method for producing ozone by ozone production system |
| CN215249573U (en) * | 2021-07-01 | 2021-12-21 | 光大水务科技发展（南京）有限公司 | Ozone separation system for generating high-concentration ozone mixed gas by using liquid oxygen |
-
2021
- 2021-07-01 CN CN202110749063.7A patent/CN113460966B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2864757A (en) * | 1956-02-17 | 1958-12-16 | Air Reduction | Ozone concentration and dilution |
| GB955825A (en) * | 1960-04-25 | 1964-04-22 | British Oxygen Co Ltd | Production of ozonised oxygen |
| EP0498585A2 (en) * | 1991-02-05 | 1992-08-12 | The BOC Group plc | Production of ozone |
| EP0560166A1 (en) * | 1992-03-10 | 1993-09-15 | Linde Aktiengesellschaft | Process and apparatus for the production of ozone |
| US5624734A (en) * | 1996-02-21 | 1997-04-29 | Rees; Darci L. | Continuous process and apparatus for generation of ozone for industrial application with cryogenic refrigeration |
| CN202864913U (en) * | 2012-09-14 | 2013-04-10 | 福建新大陆环保科技有限公司 | Ozone generation system capable of separating produced mixed gas |
| CN103663384A (en) * | 2012-09-14 | 2014-03-26 | 福建新大陆环保科技有限公司 | Method for separating mixed gas of oxygen and ozone and ozone generating system using method |
| EP3235786A1 (en) * | 2016-04-21 | 2017-10-25 | Messer Group GmbH | Device and method for generating ozone |
| CN109455672A (en) * | 2018-12-31 | 2019-03-12 | 北京清源中科环保科技有限公司 | The system and method for generating ozone and liquefaction separation using liquid oxygen |
| CN112408334A (en) * | 2020-12-02 | 2021-02-26 | 江西蓝星星火有机硅有限公司 | Ozone production system for improving ozone yield and method for producing ozone by ozone production system |
| CN215249573U (en) * | 2021-07-01 | 2021-12-21 | 光大水务科技发展（南京）有限公司 | Ozone separation system for generating high-concentration ozone mixed gas by using liquid oxygen |
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